S1

Supporting Information

Redox Active Ligand and Metal Cooperation for C(sp2)-H Oxidation Extension of Galactose Oxidase Mechanism in Water-Mediated Amide Formation

Zahra Alajia Elham Safaeia b Hong Yic Hengjiang Congc Andrzej Wojtczakd Aiwen Leic

aInstitute for Advanced Studies in Basic Sciences (IASBS) 45137-66731 Zanjan Iran

bDepartment of Chemistry College of Sciences Shiraz University 71454 Shiraz Iran Email esafaeishirazuacir

cCollege of Chemistry and Molecular Sciences Institute for Advanced Studies (IAS) Wuhan

University Wuhan Hubei 430072 P R China Email aiwenleiwhueducn

dNicolaus Copernicus University Faculty of Chemistry 87-100 Torun Poland

Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2018

S2

Content

Materials and Physical Methods

S3

Material Synthesis

S3

Figure S1 LC-MS spectrum of HLIPIP

S4

Figure S2 ESI-MS(HRMS) spectrum of CuLIPIP

S6

Figure S3 Molecular structure of CuIILIPIP S6

Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2

18O

S7

Figure S5 1H NMR of NiLAPIP-OH

S7

Figure S6 13 C NMR of NiLAPIP-OH

S8

Figure S7 ESI-MS(HRMS) spectrum of NiLAPIP-OH

S8

Figure S8 1H NMR of NiLAPIP crystals compare with NiLAPIP-OH

S9

Figure S9 EPR silent spectrum of NiIILAPIP

S10

Figure S10 Molecular structure of NiIILAPIP-MeO

S10

Figure S11 1H NMR of NiIILAPIP-MeO

S11

Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP

S11

Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca

S12

Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan rate 200 mV s CH2Cl2 298 K

S12

Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fc

S12

X-Ray Crystallography data of Copper Zinc and Nickel complexes

S13

S3

Materials and Physical Methods All reagents and solvents were purchased from commercial sources and were used as received unless noted otherwise Anhydrous Cu(OAc)2 98 Super dry acetonitrile dichloromethane were used for synthesis and growing crystal as mentioned Preparation and handling of air- and moisture-sensitive materials were carried out under an inert gas atmosphere of glove box NMR spectra were recorded at 400 MHz on a Bruker DRX spectrometer in CDCl3 solution The chemical shifts were referred to TMS using the residual signals from the solvent IR spectra were recorded in the solid state on a FT-IR Bruker Vector 22 spectrophotometer in the 400minus4000 cm-1 range LC-MS mass spectral data were acquired on Shimadzu LCMS 2020 HRMS spectra were recorded on thermo Fisher scientific LTQ Orbitrap Elite Cyclic Voltammetry (CV) was performed on CHI605E CH Instruments USA equipped with a Ag wire reference electrode a glassy carbon working electrode and a Pt counter electrode with 01 M Bu4N(BF4) solutions in CH2Cl2 Ferrocene was used as an internal standard

X-ray Crystallographic Analyses All crystals were placed onto the tip of a 01 mm diameter glass capillary and mounted on a Bruker SMART Platform CCD diffractometer for data collection The data collections were carried out using MoKαradiation with a graphite monochromator (λ= 071073 A) at 95 K Structure solutions were performed by direct methods using SHELXS-97 software and refined against F2using full-matrix-least-squares using SHELXL-97 and SHELXL-2013 software Data intensities were corrected for absorption and decay (SADABS) Final cell constants were obtained from least squares fits of all measured reflections All non-hydrogen atoms were refined with anisotropic displacement parameters

Material Synthesis To a solution of 35-DTBQ (35-di-tert-butylcyclohexa-35-diene-12-dione) (022 g 1 mmol) in acetonitrile (4 mL) was added 2-aminobenzyl amine (0122 g 1 mmol) and the reaction solution stirred for 30 min at the room temperature in the presence of air After some minutes it afforded a yellow precipitate (scheme S1) 1H NMR (400 MHz Chloroform-d) δ 870 (s 1H) 746 (dd 1H) 728 (dt 2H) 705 (d 1H) 679 (m 2H) 671 (s 1H) 627 (s 2H) 151 (s 9H) 140 (s 9H)

Scheme S1 Synthesis of HLAP ligand

Next to the stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1

mmol) (Scheme S2) LC-MS data clearly shows the formation of this ligand (Figure S1)

This ligand (HLIPIP) is stable at dry and inert condition When it is exposed on moisture it is hydrolyzed Therefore after one

minute stirring different metal precursors of copper zinc and nickel were added to reaction mixture to afford the metal

complexes (Scheme S3)

Scheme S2 Synthesis of HLIPIP ligand

S4

Figure S1 LC-MS spectrum of HLIPIP

Scheme 3 General scheme for the preparation of the different metal complexes

S5

Synthesis of CuIILAPIP

CuIILAPIP complex was synthesized by the following template reaction Firstly to the stirred suspension of HLAP (0324 g 1 mmol)

in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) after one minute stirring Cu(OAc)2H2O (0199 g 1

mmol) was added in the presence of 2 equivalents of NEt3 to the reaction mixture

The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate of copper complex The filtrate was left

undisturbed to afford red brown microcrystals (0309 g 63 yield) by evaporation from dichloromethaneacetonitrile solution

X-ray quality dark red single crystals were grown from a 11 solvent mixture of n-hexanedichloromethane Elemental Analysis

calculated (found) for C27H29N3O2Cu035 C6H14 C 6705 H 655 N 806 Found C 6679 H 661 N 776 νmax(KBr)cm-1 2959 (C-

H) 1642(C=O) 1466 (C=N) 802 (=C-H bending) ESI-MS mz 4912

Synthesis of CuIILIPIP

CuIILIPIP complex was synthesized by the following template reaction Firstly to a stirred suspension of HLAP (0324 g 1 mmol) in

dry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) Next Cu(OAc)2 (0181 g 1 mmol) was added to the

reaction mixture The stirring of orange-brown solution at 298 K for 4 h afforded a dark orange precipitate of copper complex

X-ray quality dark red single crystals from were grown from dry acetonitriledichloromethane ESI-MS mz ()4761751

Synthesis of CuIILAPIP-Meo

To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)

After one minute stirring Cu (OAc)2H2O (0199 g 1 mmol) was added in the presence of 2 equivalents of NEt3 to the reaction

mixture The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate X-ray quality dark red single

crystals were grown from a 11 solvent mixture of methanoldichloromethane

Synthesis of ZnLIPIPOAc As reported to a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1

mmol) After one minute stirring it was reacted immediately with Zn (OAc)2 2H2O (0219 g 1 mmol) to afford the zinc complex

of ZnIILIPIPOAc at the ambient temperature The stirring of black solution at 298 K for 4 h afforded a dark red-brown precipitate

X-ray quality dark crystals were grown from methanol

νmax(KBr)cm-1 3415 (OndashH) 2946 (CndashH) 1606 (C=O) 1593 (C=C) 1469 (C=N) 740 (=CndashH bending) 1H NMR (400 MHz (CD3)2SO) δ 129 (s 9H) 145 (s 9H) 159 (s 3H) 71 (d 1H) 74 (d 1H) 76 (m 2H) 78 (dd 1H) 80 (m

1H) 82 (d 1H) 84 (dt 9Hz 1H) 89 (m1H) 90(s 1H) 91(s 1H) 13C NMR (100 MHz (CD3)2SO) δ 2982 3000 3213 3221 3442 3553 10979 12103 12455 12899 12922 12963

12974 13200 13237 13354 135511385314190 145061474414999153081611716271

Synthesis of NiIILAPIP-OH

To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)

under N2 atmosphere (Figure S1) After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to

afford the nickel complex of NiIILAPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded

a precipitate ESI-MS mz ()4881843 1H NMR (400 MHz DMSO-d6) δ 880 (s 1H) 860 (dt J = 531 146 Hz 1H) 810 (td J = 769 157 Hz 1H) 777 (dd J = 741 184 Hz 2H) 764 (dd J = 761 522 Hz 2H) 737 (d J = 891 Hz 1H) 724 (ddd J = 873 663 174 Hz 1H) 696 (d J = 209 Hz 1H) 660 (ddd J = 775 660 097 Hz 1H) 634 (d J = 1012 Hz 1H) 607 (d J = 1006 Hz 1H) 145 (s 9H) 133 (s 9H) 13C NMR (101 MHz DMSO) δ 2976 3242 3460 3487 8840 11002 11387 11686 12066 12092 12491 13149 13454 14014 14114 14624 14821 14908 16014 16657

Synthesis of NiIILAPIP Solvent slow evaporation of NiLAPIP-OH solution from dichloromethaneacetonitrile afforded single crystal of NiIILAPIP ESI-MS mz

()4861880

Synthesis of NiIILIPIP

To a stirred suspension of HLAP (0324 g 1 mmol) in superdry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1

mmol) under N2 atmosphere After one minute stirring it was reacted immediately with Ni(OAc)2 (1 mmol 0176 g) to afford

the nickel complex of NiIILIPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded a

precipitate ESI-MS mz ()4711808

S6

Synthesis of NiIILAPIP-MeO

To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)

After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to afford the nickel complex at the ambient temperature The stirring of dark orange solution at 298 K for 4 h afforded a precipitate X-ray quality dark crystals were grown from dichloromethanemethanol 1H NMR (400 MHz DMSO-d6) δ 885 (s 1H) 864 (ddd J = 560 154 074 Hz 1H) 817 (td J = 767 156 Hz 1H) 787 ndash 777 (m 2H) 777 ndash 765 (m 2H) 738 (d J = 884 Hz 1H) 728 (ddd J = 873 666 176 Hz 1H) 698 (d J = 206 Hz 1H) 667 (ddd J = 786 670 101 Hz 1H) 630 (s 1H) 301 (s 3H) 145 (s 9H) 133 (s 9H)

Figures and Tables

Figure S2 ESI-MS (HRMS) spectrum of CuLIPIP

Figure S3 Molecular structure of CuIILIPIP Hydrogen atoms have been omitted for clarity Thermal ellipsoids are set at 50 probability Acetonitrile molecule with the occupancy set to 50 was also found in the structure

BCL-Z5 72 RT 048 AV 1 NL 145E3T FTMS + p ESI Full ms [5000-100000]

4759 4760 4761 4762 4763 4764 4765 4766 4767

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4761751

S7

200 300 400 500 600 700 800

0

20

40

60

80

100

Rel

ativ

e In

tens

ity

mz

49345

Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2

18O

Figure S5 1H NMR of NiLAPIP- OH

S8

Figure S6 13 C NMR of NiLAPIP-OH

Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH

BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]

4877 4878 4879 4880 4881 4882 4883 4884 4885 4886

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4881843

S9

Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)

(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to

amide)

S10

Figure S9 EPR silent spectrum of NiIILAPIP

Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are

set at 50 probability

-100000

-80000

-60000

-40000

-20000

0

20000

40000

60000

80000

100000

2500 3000 3500 4000 4500

S11

Figure S11 1H NMR of NiIILAPIP-MeO

Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP

BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]

4706 4708 4710 4712 4714 4716 4718

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4711808

S12

Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca

compound E121 V E12

2 V

CuIILAPIP +041 -166

NiIILAPIP +051 -181

ZnIILIPIPOAc +027 -147

aPeak to peak difference for the Fc+ Fc couple at 298 K is 012

Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan

rate 200 mV s CH2Cl2 298 K

Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca

compound V112E V2

12E

CuIILIPIP +021 -160

NiIILIPIP +032

-189

-25 -2 -15 -1 -05 0 05 1

S13

X-Ray Crystallography data of Copper Zinc and nickel complexes

Table S1 Crystallographic data for CuIILAPIP

CuIILAPIP

Empirical formula C27 H29 Cu N3 O2

Formula weight 49109

Crystal system Monoclinic

Space group P1 21c 1

a (Aring) 95598(5)

b (Aring) 182903(9)

c (Aring) 141699(8)

α (deg) 90

β (deg) 107231(2)

γ (deg) 90

V (Aring3) 23664(2)

Z 4

T (K) 150(2)

ρcalcd (gcm3) 1378

μ (mmndash1) 0952

Reflections collected 57791

Significant reflections 9306

R[I gt 25 (I)] 00450

Rw[I gt 25 (I)] 00999

Goodness of fit 07317

Table S2 Selected bond lengths of CuIILAPIP

Bond LAPIPCuII

Cu(1)-N(2) 1955 (1958)

Cu(1)-N(3) 1955 (1972)

Cu(1)-N(4) 1921 (1924)

Cu(1)-O(5) 1901 (1895)

C(17)-O(5) 1322 (1326)

C(22)-N(4) 1414 (1412)

C(23)-N(4) 1284 (1297)

C(6)-N(2) 1400 (1400)

C(6)-O(2) 1230 (1230)

S14

Table S3 Crystallographic data for CuIILIPIP

Table S4 Selected bond lengths of CuIILIPIP

Number Atom1 Atom2 Length

1 Cu1 N1 1965

2 Cu1 O1 1912

3 Cu1 N2 1903

4 Cu1 N3 1928

5 H1 C1 101

6 N1 C1 1343

7 N1 C5 1322

8 O1 C19 1331

9 C1 C2 1372

10 C2 H2 082

11 C2 C3 137

12 N2 C7 1366

13 N2 C6 144

14 C3 H3 085

15 C3 C4 1385

16 N3 C13 1298

17 N3 C14 1417

18 C4 H4 0995

LIPIPCuII

Empirical formula C29 H33 Cu N4 O

Formula weight 51714

Crystal system Orthorhombic

Space group Pnma

a (Aring) 24983(3)

b (Aring) 69452(7)

c (Aring) 163797(17)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 28421

Z 4

T (K) 296

ρcalcd (gcm3) 1209

μ (mmndash1) 0794

Significant reflections 6328

R[I gt 25 (I)] 00561

Rw[I gt 25 (I)] 01637

Goodness of fit 0997

S15

Table S5 Crystallographic data for CuIILAPIP-MeO

Table S6 Selected bond lengths of CuIILAPIP-MeO

Number Atom1 Atom2 Length

1 Cu1 N1 1963(2)

2 Cu1 N2 1911(2)

3 Cu1 N3 1919(2)

4 Cu1 O1 1902(2)

5 N1 C5 1333(3)

6 N1 C1 1339(4)

7 N2 C6 1429(4)

8 N2 C7 1368(3)

9 N3 C14 1423(3)

10 N3 C13 1293(3)

11 O1 C19 1320(3)

12 C4 C5 1379(4)

13 C4 C3 1367(5)

14 C4 H4 088(3)

15 C5 C6 1508(4)

16 C6 H6 109(2)

17 C6 O2 1451(3)

18 C1 C2 1368(4)

19 C1 H1 091(3)

20 C2 C3 1366(5)

CuIILAPIP-MeO

Empirical formula C28 H33 Cu N3 O2

Formula weight 50712

Crystal system Orthorhombic

Space group Pbca

a (Aring) 158660(8)

b (Aring) 145267(7)

c (Aring) 220264(11)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 507666

Z 8

T (K) 296

ρcalcd (gcm3) 1327

μ (mmndash1) 0890

Significant reflections 6328

R[I gt 25 (I)] 00470

Rw[I gt 25 (I)] 01261

Goodness of fit 0997

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S3

Materials and Physical Methods All reagents and solvents were purchased from commercial sources and were used as received unless noted otherwise Anhydrous Cu(OAc)2 98 Super dry acetonitrile dichloromethane were used for synthesis and growing crystal as mentioned Preparation and handling of air- and moisture-sensitive materials were carried out under an inert gas atmosphere of glove box NMR spectra were recorded at 400 MHz on a Bruker DRX spectrometer in CDCl3 solution The chemical shifts were referred to TMS using the residual signals from the solvent IR spectra were recorded in the solid state on a FT-IR Bruker Vector 22 spectrophotometer in the 400minus4000 cm-1 range LC-MS mass spectral data were acquired on Shimadzu LCMS 2020 HRMS spectra were recorded on thermo Fisher scientific LTQ Orbitrap Elite Cyclic Voltammetry (CV) was performed on CHI605E CH Instruments USA equipped with a Ag wire reference electrode a glassy carbon working electrode and a Pt counter electrode with 01 M Bu4N(BF4) solutions in CH2Cl2 Ferrocene was used as an internal standard

X-ray Crystallographic Analyses All crystals were placed onto the tip of a 01 mm diameter glass capillary and mounted on a Bruker SMART Platform CCD diffractometer for data collection The data collections were carried out using MoKαradiation with a graphite monochromator (λ= 071073 A) at 95 K Structure solutions were performed by direct methods using SHELXS-97 software and refined against F2using full-matrix-least-squares using SHELXL-97 and SHELXL-2013 software Data intensities were corrected for absorption and decay (SADABS) Final cell constants were obtained from least squares fits of all measured reflections All non-hydrogen atoms were refined with anisotropic displacement parameters

Material Synthesis To a solution of 35-DTBQ (35-di-tert-butylcyclohexa-35-diene-12-dione) (022 g 1 mmol) in acetonitrile (4 mL) was added 2-aminobenzyl amine (0122 g 1 mmol) and the reaction solution stirred for 30 min at the room temperature in the presence of air After some minutes it afforded a yellow precipitate (scheme S1) 1H NMR (400 MHz Chloroform-d) δ 870 (s 1H) 746 (dd 1H) 728 (dt 2H) 705 (d 1H) 679 (m 2H) 671 (s 1H) 627 (s 2H) 151 (s 9H) 140 (s 9H)

Scheme S1 Synthesis of HLAP ligand

Next to the stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1

mmol) (Scheme S2) LC-MS data clearly shows the formation of this ligand (Figure S1)

This ligand (HLIPIP) is stable at dry and inert condition When it is exposed on moisture it is hydrolyzed Therefore after one

minute stirring different metal precursors of copper zinc and nickel were added to reaction mixture to afford the metal

complexes (Scheme S3)

Scheme S2 Synthesis of HLIPIP ligand

S4

Figure S1 LC-MS spectrum of HLIPIP

Scheme 3 General scheme for the preparation of the different metal complexes

S5

Synthesis of CuIILAPIP

CuIILAPIP complex was synthesized by the following template reaction Firstly to the stirred suspension of HLAP (0324 g 1 mmol)

in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) after one minute stirring Cu(OAc)2H2O (0199 g 1

mmol) was added in the presence of 2 equivalents of NEt3 to the reaction mixture

The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate of copper complex The filtrate was left

undisturbed to afford red brown microcrystals (0309 g 63 yield) by evaporation from dichloromethaneacetonitrile solution

X-ray quality dark red single crystals were grown from a 11 solvent mixture of n-hexanedichloromethane Elemental Analysis

calculated (found) for C27H29N3O2Cu035 C6H14 C 6705 H 655 N 806 Found C 6679 H 661 N 776 νmax(KBr)cm-1 2959 (C-

H) 1642(C=O) 1466 (C=N) 802 (=C-H bending) ESI-MS mz 4912

Synthesis of CuIILIPIP

CuIILIPIP complex was synthesized by the following template reaction Firstly to a stirred suspension of HLAP (0324 g 1 mmol) in

dry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) Next Cu(OAc)2 (0181 g 1 mmol) was added to the

reaction mixture The stirring of orange-brown solution at 298 K for 4 h afforded a dark orange precipitate of copper complex

X-ray quality dark red single crystals from were grown from dry acetonitriledichloromethane ESI-MS mz ()4761751

Synthesis of CuIILAPIP-Meo

To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)

After one minute stirring Cu (OAc)2H2O (0199 g 1 mmol) was added in the presence of 2 equivalents of NEt3 to the reaction

mixture The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate X-ray quality dark red single

crystals were grown from a 11 solvent mixture of methanoldichloromethane

Synthesis of ZnLIPIPOAc As reported to a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1

mmol) After one minute stirring it was reacted immediately with Zn (OAc)2 2H2O (0219 g 1 mmol) to afford the zinc complex

of ZnIILIPIPOAc at the ambient temperature The stirring of black solution at 298 K for 4 h afforded a dark red-brown precipitate

X-ray quality dark crystals were grown from methanol

νmax(KBr)cm-1 3415 (OndashH) 2946 (CndashH) 1606 (C=O) 1593 (C=C) 1469 (C=N) 740 (=CndashH bending) 1H NMR (400 MHz (CD3)2SO) δ 129 (s 9H) 145 (s 9H) 159 (s 3H) 71 (d 1H) 74 (d 1H) 76 (m 2H) 78 (dd 1H) 80 (m

1H) 82 (d 1H) 84 (dt 9Hz 1H) 89 (m1H) 90(s 1H) 91(s 1H) 13C NMR (100 MHz (CD3)2SO) δ 2982 3000 3213 3221 3442 3553 10979 12103 12455 12899 12922 12963

12974 13200 13237 13354 135511385314190 145061474414999153081611716271

Synthesis of NiIILAPIP-OH

To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)

under N2 atmosphere (Figure S1) After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to

afford the nickel complex of NiIILAPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded

a precipitate ESI-MS mz ()4881843 1H NMR (400 MHz DMSO-d6) δ 880 (s 1H) 860 (dt J = 531 146 Hz 1H) 810 (td J = 769 157 Hz 1H) 777 (dd J = 741 184 Hz 2H) 764 (dd J = 761 522 Hz 2H) 737 (d J = 891 Hz 1H) 724 (ddd J = 873 663 174 Hz 1H) 696 (d J = 209 Hz 1H) 660 (ddd J = 775 660 097 Hz 1H) 634 (d J = 1012 Hz 1H) 607 (d J = 1006 Hz 1H) 145 (s 9H) 133 (s 9H) 13C NMR (101 MHz DMSO) δ 2976 3242 3460 3487 8840 11002 11387 11686 12066 12092 12491 13149 13454 14014 14114 14624 14821 14908 16014 16657

Synthesis of NiIILAPIP Solvent slow evaporation of NiLAPIP-OH solution from dichloromethaneacetonitrile afforded single crystal of NiIILAPIP ESI-MS mz

()4861880

Synthesis of NiIILIPIP

To a stirred suspension of HLAP (0324 g 1 mmol) in superdry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1

mmol) under N2 atmosphere After one minute stirring it was reacted immediately with Ni(OAc)2 (1 mmol 0176 g) to afford

the nickel complex of NiIILIPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded a

precipitate ESI-MS mz ()4711808

S6

Synthesis of NiIILAPIP-MeO

To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)

After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to afford the nickel complex at the ambient temperature The stirring of dark orange solution at 298 K for 4 h afforded a precipitate X-ray quality dark crystals were grown from dichloromethanemethanol 1H NMR (400 MHz DMSO-d6) δ 885 (s 1H) 864 (ddd J = 560 154 074 Hz 1H) 817 (td J = 767 156 Hz 1H) 787 ndash 777 (m 2H) 777 ndash 765 (m 2H) 738 (d J = 884 Hz 1H) 728 (ddd J = 873 666 176 Hz 1H) 698 (d J = 206 Hz 1H) 667 (ddd J = 786 670 101 Hz 1H) 630 (s 1H) 301 (s 3H) 145 (s 9H) 133 (s 9H)

Figures and Tables

Figure S2 ESI-MS (HRMS) spectrum of CuLIPIP

Figure S3 Molecular structure of CuIILIPIP Hydrogen atoms have been omitted for clarity Thermal ellipsoids are set at 50 probability Acetonitrile molecule with the occupancy set to 50 was also found in the structure

BCL-Z5 72 RT 048 AV 1 NL 145E3T FTMS + p ESI Full ms [5000-100000]

4759 4760 4761 4762 4763 4764 4765 4766 4767

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4761751

S7

200 300 400 500 600 700 800

0

20

40

60

80

100

Rel

ativ

e In

tens

ity

mz

49345

Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2

18O

Figure S5 1H NMR of NiLAPIP- OH

S8

Figure S6 13 C NMR of NiLAPIP-OH

Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH

BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]

4877 4878 4879 4880 4881 4882 4883 4884 4885 4886

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4881843

S9

Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)

(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to

amide)

S10

Figure S9 EPR silent spectrum of NiIILAPIP

Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are

set at 50 probability

-100000

-80000

-60000

-40000

-20000

0

20000

40000

60000

80000

100000

2500 3000 3500 4000 4500

S11

Figure S11 1H NMR of NiIILAPIP-MeO

Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP

BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]

4706 4708 4710 4712 4714 4716 4718

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4711808

S12

Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca

compound E121 V E12

2 V

CuIILAPIP +041 -166

NiIILAPIP +051 -181

ZnIILIPIPOAc +027 -147

aPeak to peak difference for the Fc+ Fc couple at 298 K is 012

Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan

rate 200 mV s CH2Cl2 298 K

Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca

compound V112E V2

12E

CuIILIPIP +021 -160

NiIILIPIP +032

-189

-25 -2 -15 -1 -05 0 05 1

S13

X-Ray Crystallography data of Copper Zinc and nickel complexes

Table S1 Crystallographic data for CuIILAPIP

CuIILAPIP

Empirical formula C27 H29 Cu N3 O2

Formula weight 49109

Crystal system Monoclinic

Space group P1 21c 1

a (Aring) 95598(5)

b (Aring) 182903(9)

c (Aring) 141699(8)

α (deg) 90

β (deg) 107231(2)

γ (deg) 90

V (Aring3) 23664(2)

Z 4

T (K) 150(2)

ρcalcd (gcm3) 1378

μ (mmndash1) 0952

Reflections collected 57791

Significant reflections 9306

R[I gt 25 (I)] 00450

Rw[I gt 25 (I)] 00999

Goodness of fit 07317

Table S2 Selected bond lengths of CuIILAPIP

Bond LAPIPCuII

Cu(1)-N(2) 1955 (1958)

Cu(1)-N(3) 1955 (1972)

Cu(1)-N(4) 1921 (1924)

Cu(1)-O(5) 1901 (1895)

C(17)-O(5) 1322 (1326)

C(22)-N(4) 1414 (1412)

C(23)-N(4) 1284 (1297)

C(6)-N(2) 1400 (1400)

C(6)-O(2) 1230 (1230)

S14

Table S3 Crystallographic data for CuIILIPIP

Table S4 Selected bond lengths of CuIILIPIP

Number Atom1 Atom2 Length

1 Cu1 N1 1965

2 Cu1 O1 1912

3 Cu1 N2 1903

4 Cu1 N3 1928

5 H1 C1 101

6 N1 C1 1343

7 N1 C5 1322

8 O1 C19 1331

9 C1 C2 1372

10 C2 H2 082

11 C2 C3 137

12 N2 C7 1366

13 N2 C6 144

14 C3 H3 085

15 C3 C4 1385

16 N3 C13 1298

17 N3 C14 1417

18 C4 H4 0995

LIPIPCuII

Empirical formula C29 H33 Cu N4 O

Formula weight 51714

Crystal system Orthorhombic

Space group Pnma

a (Aring) 24983(3)

b (Aring) 69452(7)

c (Aring) 163797(17)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 28421

Z 4

T (K) 296

ρcalcd (gcm3) 1209

μ (mmndash1) 0794

Significant reflections 6328

R[I gt 25 (I)] 00561

Rw[I gt 25 (I)] 01637

Goodness of fit 0997

S15

Table S5 Crystallographic data for CuIILAPIP-MeO

Table S6 Selected bond lengths of CuIILAPIP-MeO

Number Atom1 Atom2 Length

1 Cu1 N1 1963(2)

2 Cu1 N2 1911(2)

3 Cu1 N3 1919(2)

4 Cu1 O1 1902(2)

5 N1 C5 1333(3)

6 N1 C1 1339(4)

7 N2 C6 1429(4)

8 N2 C7 1368(3)

9 N3 C14 1423(3)

10 N3 C13 1293(3)

11 O1 C19 1320(3)

12 C4 C5 1379(4)

13 C4 C3 1367(5)

14 C4 H4 088(3)

15 C5 C6 1508(4)

16 C6 H6 109(2)

17 C6 O2 1451(3)

18 C1 C2 1368(4)

19 C1 H1 091(3)

20 C2 C3 1366(5)

CuIILAPIP-MeO

Empirical formula C28 H33 Cu N3 O2

Formula weight 50712

Crystal system Orthorhombic

Space group Pbca

a (Aring) 158660(8)

b (Aring) 145267(7)

c (Aring) 220264(11)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 507666

Z 8

T (K) 296

ρcalcd (gcm3) 1327

μ (mmndash1) 0890

Significant reflections 6328

R[I gt 25 (I)] 00470

Rw[I gt 25 (I)] 01261

Goodness of fit 0997

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S4

Figure S1 LC-MS spectrum of HLIPIP

Scheme 3 General scheme for the preparation of the different metal complexes

S5

Synthesis of CuIILAPIP

CuIILAPIP complex was synthesized by the following template reaction Firstly to the stirred suspension of HLAP (0324 g 1 mmol)

in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) after one minute stirring Cu(OAc)2H2O (0199 g 1

mmol) was added in the presence of 2 equivalents of NEt3 to the reaction mixture

The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate of copper complex The filtrate was left

undisturbed to afford red brown microcrystals (0309 g 63 yield) by evaporation from dichloromethaneacetonitrile solution

X-ray quality dark red single crystals were grown from a 11 solvent mixture of n-hexanedichloromethane Elemental Analysis

calculated (found) for C27H29N3O2Cu035 C6H14 C 6705 H 655 N 806 Found C 6679 H 661 N 776 νmax(KBr)cm-1 2959 (C-

H) 1642(C=O) 1466 (C=N) 802 (=C-H bending) ESI-MS mz 4912

Synthesis of CuIILIPIP

CuIILIPIP complex was synthesized by the following template reaction Firstly to a stirred suspension of HLAP (0324 g 1 mmol) in

dry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) Next Cu(OAc)2 (0181 g 1 mmol) was added to the

reaction mixture The stirring of orange-brown solution at 298 K for 4 h afforded a dark orange precipitate of copper complex

X-ray quality dark red single crystals from were grown from dry acetonitriledichloromethane ESI-MS mz ()4761751

Synthesis of CuIILAPIP-Meo

To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)

After one minute stirring Cu (OAc)2H2O (0199 g 1 mmol) was added in the presence of 2 equivalents of NEt3 to the reaction

mixture The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate X-ray quality dark red single

crystals were grown from a 11 solvent mixture of methanoldichloromethane

Synthesis of ZnLIPIPOAc As reported to a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1

mmol) After one minute stirring it was reacted immediately with Zn (OAc)2 2H2O (0219 g 1 mmol) to afford the zinc complex

of ZnIILIPIPOAc at the ambient temperature The stirring of black solution at 298 K for 4 h afforded a dark red-brown precipitate

X-ray quality dark crystals were grown from methanol

νmax(KBr)cm-1 3415 (OndashH) 2946 (CndashH) 1606 (C=O) 1593 (C=C) 1469 (C=N) 740 (=CndashH bending) 1H NMR (400 MHz (CD3)2SO) δ 129 (s 9H) 145 (s 9H) 159 (s 3H) 71 (d 1H) 74 (d 1H) 76 (m 2H) 78 (dd 1H) 80 (m

1H) 82 (d 1H) 84 (dt 9Hz 1H) 89 (m1H) 90(s 1H) 91(s 1H) 13C NMR (100 MHz (CD3)2SO) δ 2982 3000 3213 3221 3442 3553 10979 12103 12455 12899 12922 12963

12974 13200 13237 13354 135511385314190 145061474414999153081611716271

Synthesis of NiIILAPIP-OH

To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)

under N2 atmosphere (Figure S1) After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to

afford the nickel complex of NiIILAPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded

a precipitate ESI-MS mz ()4881843 1H NMR (400 MHz DMSO-d6) δ 880 (s 1H) 860 (dt J = 531 146 Hz 1H) 810 (td J = 769 157 Hz 1H) 777 (dd J = 741 184 Hz 2H) 764 (dd J = 761 522 Hz 2H) 737 (d J = 891 Hz 1H) 724 (ddd J = 873 663 174 Hz 1H) 696 (d J = 209 Hz 1H) 660 (ddd J = 775 660 097 Hz 1H) 634 (d J = 1012 Hz 1H) 607 (d J = 1006 Hz 1H) 145 (s 9H) 133 (s 9H) 13C NMR (101 MHz DMSO) δ 2976 3242 3460 3487 8840 11002 11387 11686 12066 12092 12491 13149 13454 14014 14114 14624 14821 14908 16014 16657

Synthesis of NiIILAPIP Solvent slow evaporation of NiLAPIP-OH solution from dichloromethaneacetonitrile afforded single crystal of NiIILAPIP ESI-MS mz

()4861880

Synthesis of NiIILIPIP

To a stirred suspension of HLAP (0324 g 1 mmol) in superdry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1

mmol) under N2 atmosphere After one minute stirring it was reacted immediately with Ni(OAc)2 (1 mmol 0176 g) to afford

the nickel complex of NiIILIPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded a

precipitate ESI-MS mz ()4711808

S6

Synthesis of NiIILAPIP-MeO

To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)

After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to afford the nickel complex at the ambient temperature The stirring of dark orange solution at 298 K for 4 h afforded a precipitate X-ray quality dark crystals were grown from dichloromethanemethanol 1H NMR (400 MHz DMSO-d6) δ 885 (s 1H) 864 (ddd J = 560 154 074 Hz 1H) 817 (td J = 767 156 Hz 1H) 787 ndash 777 (m 2H) 777 ndash 765 (m 2H) 738 (d J = 884 Hz 1H) 728 (ddd J = 873 666 176 Hz 1H) 698 (d J = 206 Hz 1H) 667 (ddd J = 786 670 101 Hz 1H) 630 (s 1H) 301 (s 3H) 145 (s 9H) 133 (s 9H)

Figures and Tables

Figure S2 ESI-MS (HRMS) spectrum of CuLIPIP

Figure S3 Molecular structure of CuIILIPIP Hydrogen atoms have been omitted for clarity Thermal ellipsoids are set at 50 probability Acetonitrile molecule with the occupancy set to 50 was also found in the structure

BCL-Z5 72 RT 048 AV 1 NL 145E3T FTMS + p ESI Full ms [5000-100000]

4759 4760 4761 4762 4763 4764 4765 4766 4767

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4761751

S7

200 300 400 500 600 700 800

0

20

40

60

80

100

Rel

ativ

e In

tens

ity

mz

49345

Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2

18O

Figure S5 1H NMR of NiLAPIP- OH

S8

Figure S6 13 C NMR of NiLAPIP-OH

Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH

BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]

4877 4878 4879 4880 4881 4882 4883 4884 4885 4886

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4881843

S9

Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)

(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to

amide)

S10

Figure S9 EPR silent spectrum of NiIILAPIP

Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are

set at 50 probability

-100000

-80000

-60000

-40000

-20000

0

20000

40000

60000

80000

100000

2500 3000 3500 4000 4500

S11

Figure S11 1H NMR of NiIILAPIP-MeO

Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP

BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]

4706 4708 4710 4712 4714 4716 4718

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4711808

S12

Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca

compound E121 V E12

2 V

CuIILAPIP +041 -166

NiIILAPIP +051 -181

ZnIILIPIPOAc +027 -147

aPeak to peak difference for the Fc+ Fc couple at 298 K is 012

Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan

rate 200 mV s CH2Cl2 298 K

Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca

compound V112E V2

12E

CuIILIPIP +021 -160

NiIILIPIP +032

-189

-25 -2 -15 -1 -05 0 05 1

S13

X-Ray Crystallography data of Copper Zinc and nickel complexes

Table S1 Crystallographic data for CuIILAPIP

CuIILAPIP

Empirical formula C27 H29 Cu N3 O2

Formula weight 49109

Crystal system Monoclinic

Space group P1 21c 1

a (Aring) 95598(5)

b (Aring) 182903(9)

c (Aring) 141699(8)

α (deg) 90

β (deg) 107231(2)

γ (deg) 90

V (Aring3) 23664(2)

Z 4

T (K) 150(2)

ρcalcd (gcm3) 1378

μ (mmndash1) 0952

Reflections collected 57791

Significant reflections 9306

R[I gt 25 (I)] 00450

Rw[I gt 25 (I)] 00999

Goodness of fit 07317

Table S2 Selected bond lengths of CuIILAPIP

Bond LAPIPCuII

Cu(1)-N(2) 1955 (1958)

Cu(1)-N(3) 1955 (1972)

Cu(1)-N(4) 1921 (1924)

Cu(1)-O(5) 1901 (1895)

C(17)-O(5) 1322 (1326)

C(22)-N(4) 1414 (1412)

C(23)-N(4) 1284 (1297)

C(6)-N(2) 1400 (1400)

C(6)-O(2) 1230 (1230)

S14

Table S3 Crystallographic data for CuIILIPIP

Table S4 Selected bond lengths of CuIILIPIP

Number Atom1 Atom2 Length

1 Cu1 N1 1965

2 Cu1 O1 1912

3 Cu1 N2 1903

4 Cu1 N3 1928

5 H1 C1 101

6 N1 C1 1343

7 N1 C5 1322

8 O1 C19 1331

9 C1 C2 1372

10 C2 H2 082

11 C2 C3 137

12 N2 C7 1366

13 N2 C6 144

14 C3 H3 085

15 C3 C4 1385

16 N3 C13 1298

17 N3 C14 1417

18 C4 H4 0995

LIPIPCuII

Empirical formula C29 H33 Cu N4 O

Formula weight 51714

Crystal system Orthorhombic

Space group Pnma

a (Aring) 24983(3)

b (Aring) 69452(7)

c (Aring) 163797(17)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 28421

Z 4

T (K) 296

ρcalcd (gcm3) 1209

μ (mmndash1) 0794

Significant reflections 6328

R[I gt 25 (I)] 00561

Rw[I gt 25 (I)] 01637

Goodness of fit 0997

S15

Table S5 Crystallographic data for CuIILAPIP-MeO

Table S6 Selected bond lengths of CuIILAPIP-MeO

Number Atom1 Atom2 Length

1 Cu1 N1 1963(2)

2 Cu1 N2 1911(2)

3 Cu1 N3 1919(2)

4 Cu1 O1 1902(2)

5 N1 C5 1333(3)

6 N1 C1 1339(4)

7 N2 C6 1429(4)

8 N2 C7 1368(3)

9 N3 C14 1423(3)

10 N3 C13 1293(3)

11 O1 C19 1320(3)

12 C4 C5 1379(4)

13 C4 C3 1367(5)

14 C4 H4 088(3)

15 C5 C6 1508(4)

16 C6 H6 109(2)

17 C6 O2 1451(3)

18 C1 C2 1368(4)

19 C1 H1 091(3)

20 C2 C3 1366(5)

CuIILAPIP-MeO

Empirical formula C28 H33 Cu N3 O2

Formula weight 50712

Crystal system Orthorhombic

Space group Pbca

a (Aring) 158660(8)

b (Aring) 145267(7)

c (Aring) 220264(11)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 507666

Z 8

T (K) 296

ρcalcd (gcm3) 1327

μ (mmndash1) 0890

Significant reflections 6328

R[I gt 25 (I)] 00470

Rw[I gt 25 (I)] 01261

Goodness of fit 0997

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S5

Synthesis of CuIILAPIP

CuIILAPIP complex was synthesized by the following template reaction Firstly to the stirred suspension of HLAP (0324 g 1 mmol)

in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) after one minute stirring Cu(OAc)2H2O (0199 g 1

mmol) was added in the presence of 2 equivalents of NEt3 to the reaction mixture

The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate of copper complex The filtrate was left

undisturbed to afford red brown microcrystals (0309 g 63 yield) by evaporation from dichloromethaneacetonitrile solution

X-ray quality dark red single crystals were grown from a 11 solvent mixture of n-hexanedichloromethane Elemental Analysis

calculated (found) for C27H29N3O2Cu035 C6H14 C 6705 H 655 N 806 Found C 6679 H 661 N 776 νmax(KBr)cm-1 2959 (C-

H) 1642(C=O) 1466 (C=N) 802 (=C-H bending) ESI-MS mz 4912

Synthesis of CuIILIPIP

CuIILIPIP complex was synthesized by the following template reaction Firstly to a stirred suspension of HLAP (0324 g 1 mmol) in

dry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) Next Cu(OAc)2 (0181 g 1 mmol) was added to the

reaction mixture The stirring of orange-brown solution at 298 K for 4 h afforded a dark orange precipitate of copper complex

X-ray quality dark red single crystals from were grown from dry acetonitriledichloromethane ESI-MS mz ()4761751

Synthesis of CuIILAPIP-Meo

To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)

After one minute stirring Cu (OAc)2H2O (0199 g 1 mmol) was added in the presence of 2 equivalents of NEt3 to the reaction

mixture The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate X-ray quality dark red single

crystals were grown from a 11 solvent mixture of methanoldichloromethane

Synthesis of ZnLIPIPOAc As reported to a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1

mmol) After one minute stirring it was reacted immediately with Zn (OAc)2 2H2O (0219 g 1 mmol) to afford the zinc complex

of ZnIILIPIPOAc at the ambient temperature The stirring of black solution at 298 K for 4 h afforded a dark red-brown precipitate

X-ray quality dark crystals were grown from methanol

νmax(KBr)cm-1 3415 (OndashH) 2946 (CndashH) 1606 (C=O) 1593 (C=C) 1469 (C=N) 740 (=CndashH bending) 1H NMR (400 MHz (CD3)2SO) δ 129 (s 9H) 145 (s 9H) 159 (s 3H) 71 (d 1H) 74 (d 1H) 76 (m 2H) 78 (dd 1H) 80 (m

1H) 82 (d 1H) 84 (dt 9Hz 1H) 89 (m1H) 90(s 1H) 91(s 1H) 13C NMR (100 MHz (CD3)2SO) δ 2982 3000 3213 3221 3442 3553 10979 12103 12455 12899 12922 12963

12974 13200 13237 13354 135511385314190 145061474414999153081611716271

Synthesis of NiIILAPIP-OH

To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)

under N2 atmosphere (Figure S1) After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to

afford the nickel complex of NiIILAPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded

a precipitate ESI-MS mz ()4881843 1H NMR (400 MHz DMSO-d6) δ 880 (s 1H) 860 (dt J = 531 146 Hz 1H) 810 (td J = 769 157 Hz 1H) 777 (dd J = 741 184 Hz 2H) 764 (dd J = 761 522 Hz 2H) 737 (d J = 891 Hz 1H) 724 (ddd J = 873 663 174 Hz 1H) 696 (d J = 209 Hz 1H) 660 (ddd J = 775 660 097 Hz 1H) 634 (d J = 1012 Hz 1H) 607 (d J = 1006 Hz 1H) 145 (s 9H) 133 (s 9H) 13C NMR (101 MHz DMSO) δ 2976 3242 3460 3487 8840 11002 11387 11686 12066 12092 12491 13149 13454 14014 14114 14624 14821 14908 16014 16657

Synthesis of NiIILAPIP Solvent slow evaporation of NiLAPIP-OH solution from dichloromethaneacetonitrile afforded single crystal of NiIILAPIP ESI-MS mz

()4861880

Synthesis of NiIILIPIP

To a stirred suspension of HLAP (0324 g 1 mmol) in superdry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1

mmol) under N2 atmosphere After one minute stirring it was reacted immediately with Ni(OAc)2 (1 mmol 0176 g) to afford

the nickel complex of NiIILIPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded a

precipitate ESI-MS mz ()4711808

S6

Synthesis of NiIILAPIP-MeO

To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)

After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to afford the nickel complex at the ambient temperature The stirring of dark orange solution at 298 K for 4 h afforded a precipitate X-ray quality dark crystals were grown from dichloromethanemethanol 1H NMR (400 MHz DMSO-d6) δ 885 (s 1H) 864 (ddd J = 560 154 074 Hz 1H) 817 (td J = 767 156 Hz 1H) 787 ndash 777 (m 2H) 777 ndash 765 (m 2H) 738 (d J = 884 Hz 1H) 728 (ddd J = 873 666 176 Hz 1H) 698 (d J = 206 Hz 1H) 667 (ddd J = 786 670 101 Hz 1H) 630 (s 1H) 301 (s 3H) 145 (s 9H) 133 (s 9H)

Figures and Tables

Figure S2 ESI-MS (HRMS) spectrum of CuLIPIP

Figure S3 Molecular structure of CuIILIPIP Hydrogen atoms have been omitted for clarity Thermal ellipsoids are set at 50 probability Acetonitrile molecule with the occupancy set to 50 was also found in the structure

BCL-Z5 72 RT 048 AV 1 NL 145E3T FTMS + p ESI Full ms [5000-100000]

4759 4760 4761 4762 4763 4764 4765 4766 4767

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4761751

S7

200 300 400 500 600 700 800

0

20

40

60

80

100

Rel

ativ

e In

tens

ity

mz

49345

Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2

18O

Figure S5 1H NMR of NiLAPIP- OH

S8

Figure S6 13 C NMR of NiLAPIP-OH

Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH

BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]

4877 4878 4879 4880 4881 4882 4883 4884 4885 4886

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4881843

S9

Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)

(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to

amide)

S10

Figure S9 EPR silent spectrum of NiIILAPIP

Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are

set at 50 probability

-100000

-80000

-60000

-40000

-20000

0

20000

40000

60000

80000

100000

2500 3000 3500 4000 4500

S11

Figure S11 1H NMR of NiIILAPIP-MeO

Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP

BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]

4706 4708 4710 4712 4714 4716 4718

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4711808

S12

Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca

compound E121 V E12

2 V

CuIILAPIP +041 -166

NiIILAPIP +051 -181

ZnIILIPIPOAc +027 -147

aPeak to peak difference for the Fc+ Fc couple at 298 K is 012

Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan

rate 200 mV s CH2Cl2 298 K

Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca

compound V112E V2

12E

CuIILIPIP +021 -160

NiIILIPIP +032

-189

-25 -2 -15 -1 -05 0 05 1

S13

X-Ray Crystallography data of Copper Zinc and nickel complexes

Table S1 Crystallographic data for CuIILAPIP

CuIILAPIP

Empirical formula C27 H29 Cu N3 O2

Formula weight 49109

Crystal system Monoclinic

Space group P1 21c 1

a (Aring) 95598(5)

b (Aring) 182903(9)

c (Aring) 141699(8)

α (deg) 90

β (deg) 107231(2)

γ (deg) 90

V (Aring3) 23664(2)

Z 4

T (K) 150(2)

ρcalcd (gcm3) 1378

μ (mmndash1) 0952

Reflections collected 57791

Significant reflections 9306

R[I gt 25 (I)] 00450

Rw[I gt 25 (I)] 00999

Goodness of fit 07317

Table S2 Selected bond lengths of CuIILAPIP

Bond LAPIPCuII

Cu(1)-N(2) 1955 (1958)

Cu(1)-N(3) 1955 (1972)

Cu(1)-N(4) 1921 (1924)

Cu(1)-O(5) 1901 (1895)

C(17)-O(5) 1322 (1326)

C(22)-N(4) 1414 (1412)

C(23)-N(4) 1284 (1297)

C(6)-N(2) 1400 (1400)

C(6)-O(2) 1230 (1230)

S14

Table S3 Crystallographic data for CuIILIPIP

Table S4 Selected bond lengths of CuIILIPIP

Number Atom1 Atom2 Length

1 Cu1 N1 1965

2 Cu1 O1 1912

3 Cu1 N2 1903

4 Cu1 N3 1928

5 H1 C1 101

6 N1 C1 1343

7 N1 C5 1322

8 O1 C19 1331

9 C1 C2 1372

10 C2 H2 082

11 C2 C3 137

12 N2 C7 1366

13 N2 C6 144

14 C3 H3 085

15 C3 C4 1385

16 N3 C13 1298

17 N3 C14 1417

18 C4 H4 0995

LIPIPCuII

Empirical formula C29 H33 Cu N4 O

Formula weight 51714

Crystal system Orthorhombic

Space group Pnma

a (Aring) 24983(3)

b (Aring) 69452(7)

c (Aring) 163797(17)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 28421

Z 4

T (K) 296

ρcalcd (gcm3) 1209

μ (mmndash1) 0794

Significant reflections 6328

R[I gt 25 (I)] 00561

Rw[I gt 25 (I)] 01637

Goodness of fit 0997

S15

Table S5 Crystallographic data for CuIILAPIP-MeO

Table S6 Selected bond lengths of CuIILAPIP-MeO

Number Atom1 Atom2 Length

1 Cu1 N1 1963(2)

2 Cu1 N2 1911(2)

3 Cu1 N3 1919(2)

4 Cu1 O1 1902(2)

5 N1 C5 1333(3)

6 N1 C1 1339(4)

7 N2 C6 1429(4)

8 N2 C7 1368(3)

9 N3 C14 1423(3)

10 N3 C13 1293(3)

11 O1 C19 1320(3)

12 C4 C5 1379(4)

13 C4 C3 1367(5)

14 C4 H4 088(3)

15 C5 C6 1508(4)

16 C6 H6 109(2)

17 C6 O2 1451(3)

18 C1 C2 1368(4)

19 C1 H1 091(3)

20 C2 C3 1366(5)

CuIILAPIP-MeO

Empirical formula C28 H33 Cu N3 O2

Formula weight 50712

Crystal system Orthorhombic

Space group Pbca

a (Aring) 158660(8)

b (Aring) 145267(7)

c (Aring) 220264(11)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 507666

Z 8

T (K) 296

ρcalcd (gcm3) 1327

μ (mmndash1) 0890

Significant reflections 6328

R[I gt 25 (I)] 00470

Rw[I gt 25 (I)] 01261

Goodness of fit 0997

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S6

Synthesis of NiIILAPIP-MeO

To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)

After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to afford the nickel complex at the ambient temperature The stirring of dark orange solution at 298 K for 4 h afforded a precipitate X-ray quality dark crystals were grown from dichloromethanemethanol 1H NMR (400 MHz DMSO-d6) δ 885 (s 1H) 864 (ddd J = 560 154 074 Hz 1H) 817 (td J = 767 156 Hz 1H) 787 ndash 777 (m 2H) 777 ndash 765 (m 2H) 738 (d J = 884 Hz 1H) 728 (ddd J = 873 666 176 Hz 1H) 698 (d J = 206 Hz 1H) 667 (ddd J = 786 670 101 Hz 1H) 630 (s 1H) 301 (s 3H) 145 (s 9H) 133 (s 9H)

Figures and Tables

Figure S2 ESI-MS (HRMS) spectrum of CuLIPIP

Figure S3 Molecular structure of CuIILIPIP Hydrogen atoms have been omitted for clarity Thermal ellipsoids are set at 50 probability Acetonitrile molecule with the occupancy set to 50 was also found in the structure

BCL-Z5 72 RT 048 AV 1 NL 145E3T FTMS + p ESI Full ms [5000-100000]

4759 4760 4761 4762 4763 4764 4765 4766 4767

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4761751

S7

200 300 400 500 600 700 800

0

20

40

60

80

100

Rel

ativ

e In

tens

ity

mz

49345

Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2

18O

Figure S5 1H NMR of NiLAPIP- OH

S8

Figure S6 13 C NMR of NiLAPIP-OH

Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH

BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]

4877 4878 4879 4880 4881 4882 4883 4884 4885 4886

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4881843

S9

Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)

(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to

amide)

S10

Figure S9 EPR silent spectrum of NiIILAPIP

Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are

set at 50 probability

-100000

-80000

-60000

-40000

-20000

0

20000

40000

60000

80000

100000

2500 3000 3500 4000 4500

S11

Figure S11 1H NMR of NiIILAPIP-MeO

Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP

BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]

4706 4708 4710 4712 4714 4716 4718

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4711808

S12

Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca

compound E121 V E12

2 V

CuIILAPIP +041 -166

NiIILAPIP +051 -181

ZnIILIPIPOAc +027 -147

aPeak to peak difference for the Fc+ Fc couple at 298 K is 012

Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan

rate 200 mV s CH2Cl2 298 K

Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca

compound V112E V2

12E

CuIILIPIP +021 -160

NiIILIPIP +032

-189

-25 -2 -15 -1 -05 0 05 1

S13

X-Ray Crystallography data of Copper Zinc and nickel complexes

Table S1 Crystallographic data for CuIILAPIP

CuIILAPIP

Empirical formula C27 H29 Cu N3 O2

Formula weight 49109

Crystal system Monoclinic

Space group P1 21c 1

a (Aring) 95598(5)

b (Aring) 182903(9)

c (Aring) 141699(8)

α (deg) 90

β (deg) 107231(2)

γ (deg) 90

V (Aring3) 23664(2)

Z 4

T (K) 150(2)

ρcalcd (gcm3) 1378

μ (mmndash1) 0952

Reflections collected 57791

Significant reflections 9306

R[I gt 25 (I)] 00450

Rw[I gt 25 (I)] 00999

Goodness of fit 07317

Table S2 Selected bond lengths of CuIILAPIP

Bond LAPIPCuII

Cu(1)-N(2) 1955 (1958)

Cu(1)-N(3) 1955 (1972)

Cu(1)-N(4) 1921 (1924)

Cu(1)-O(5) 1901 (1895)

C(17)-O(5) 1322 (1326)

C(22)-N(4) 1414 (1412)

C(23)-N(4) 1284 (1297)

C(6)-N(2) 1400 (1400)

C(6)-O(2) 1230 (1230)

S14

Table S3 Crystallographic data for CuIILIPIP

Table S4 Selected bond lengths of CuIILIPIP

Number Atom1 Atom2 Length

1 Cu1 N1 1965

2 Cu1 O1 1912

3 Cu1 N2 1903

4 Cu1 N3 1928

5 H1 C1 101

6 N1 C1 1343

7 N1 C5 1322

8 O1 C19 1331

9 C1 C2 1372

10 C2 H2 082

11 C2 C3 137

12 N2 C7 1366

13 N2 C6 144

14 C3 H3 085

15 C3 C4 1385

16 N3 C13 1298

17 N3 C14 1417

18 C4 H4 0995

LIPIPCuII

Empirical formula C29 H33 Cu N4 O

Formula weight 51714

Crystal system Orthorhombic

Space group Pnma

a (Aring) 24983(3)

b (Aring) 69452(7)

c (Aring) 163797(17)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 28421

Z 4

T (K) 296

ρcalcd (gcm3) 1209

μ (mmndash1) 0794

Significant reflections 6328

R[I gt 25 (I)] 00561

Rw[I gt 25 (I)] 01637

Goodness of fit 0997

S15

Table S5 Crystallographic data for CuIILAPIP-MeO

Table S6 Selected bond lengths of CuIILAPIP-MeO

Number Atom1 Atom2 Length

1 Cu1 N1 1963(2)

2 Cu1 N2 1911(2)

3 Cu1 N3 1919(2)

4 Cu1 O1 1902(2)

5 N1 C5 1333(3)

6 N1 C1 1339(4)

7 N2 C6 1429(4)

8 N2 C7 1368(3)

9 N3 C14 1423(3)

10 N3 C13 1293(3)

11 O1 C19 1320(3)

12 C4 C5 1379(4)

13 C4 C3 1367(5)

14 C4 H4 088(3)

15 C5 C6 1508(4)

16 C6 H6 109(2)

17 C6 O2 1451(3)

18 C1 C2 1368(4)

19 C1 H1 091(3)

20 C2 C3 1366(5)

CuIILAPIP-MeO

Empirical formula C28 H33 Cu N3 O2

Formula weight 50712

Crystal system Orthorhombic

Space group Pbca

a (Aring) 158660(8)

b (Aring) 145267(7)

c (Aring) 220264(11)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 507666

Z 8

T (K) 296

ρcalcd (gcm3) 1327

μ (mmndash1) 0890

Significant reflections 6328

R[I gt 25 (I)] 00470

Rw[I gt 25 (I)] 01261

Goodness of fit 0997

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S7

200 300 400 500 600 700 800

0

20

40

60

80

100

Rel

ativ

e In

tens

ity

mz

49345

Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2

18O

Figure S5 1H NMR of NiLAPIP- OH

S8

Figure S6 13 C NMR of NiLAPIP-OH

Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH

BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]

4877 4878 4879 4880 4881 4882 4883 4884 4885 4886

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4881843

S9

Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)

(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to

amide)

S10

Figure S9 EPR silent spectrum of NiIILAPIP

Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are

set at 50 probability

-100000

-80000

-60000

-40000

-20000

0

20000

40000

60000

80000

100000

2500 3000 3500 4000 4500

S11

Figure S11 1H NMR of NiIILAPIP-MeO

Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP

BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]

4706 4708 4710 4712 4714 4716 4718

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4711808

S12

Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca

compound E121 V E12

2 V

CuIILAPIP +041 -166

NiIILAPIP +051 -181

ZnIILIPIPOAc +027 -147

aPeak to peak difference for the Fc+ Fc couple at 298 K is 012

Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan

rate 200 mV s CH2Cl2 298 K

Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca

compound V112E V2

12E

CuIILIPIP +021 -160

NiIILIPIP +032

-189

-25 -2 -15 -1 -05 0 05 1

S13

X-Ray Crystallography data of Copper Zinc and nickel complexes

Table S1 Crystallographic data for CuIILAPIP

CuIILAPIP

Empirical formula C27 H29 Cu N3 O2

Formula weight 49109

Crystal system Monoclinic

Space group P1 21c 1

a (Aring) 95598(5)

b (Aring) 182903(9)

c (Aring) 141699(8)

α (deg) 90

β (deg) 107231(2)

γ (deg) 90

V (Aring3) 23664(2)

Z 4

T (K) 150(2)

ρcalcd (gcm3) 1378

μ (mmndash1) 0952

Reflections collected 57791

Significant reflections 9306

R[I gt 25 (I)] 00450

Rw[I gt 25 (I)] 00999

Goodness of fit 07317

Table S2 Selected bond lengths of CuIILAPIP

Bond LAPIPCuII

Cu(1)-N(2) 1955 (1958)

Cu(1)-N(3) 1955 (1972)

Cu(1)-N(4) 1921 (1924)

Cu(1)-O(5) 1901 (1895)

C(17)-O(5) 1322 (1326)

C(22)-N(4) 1414 (1412)

C(23)-N(4) 1284 (1297)

C(6)-N(2) 1400 (1400)

C(6)-O(2) 1230 (1230)

S14

Table S3 Crystallographic data for CuIILIPIP

Table S4 Selected bond lengths of CuIILIPIP

Number Atom1 Atom2 Length

1 Cu1 N1 1965

2 Cu1 O1 1912

3 Cu1 N2 1903

4 Cu1 N3 1928

5 H1 C1 101

6 N1 C1 1343

7 N1 C5 1322

8 O1 C19 1331

9 C1 C2 1372

10 C2 H2 082

11 C2 C3 137

12 N2 C7 1366

13 N2 C6 144

14 C3 H3 085

15 C3 C4 1385

16 N3 C13 1298

17 N3 C14 1417

18 C4 H4 0995

LIPIPCuII

Empirical formula C29 H33 Cu N4 O

Formula weight 51714

Crystal system Orthorhombic

Space group Pnma

a (Aring) 24983(3)

b (Aring) 69452(7)

c (Aring) 163797(17)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 28421

Z 4

T (K) 296

ρcalcd (gcm3) 1209

μ (mmndash1) 0794

Significant reflections 6328

R[I gt 25 (I)] 00561

Rw[I gt 25 (I)] 01637

Goodness of fit 0997

S15

Table S5 Crystallographic data for CuIILAPIP-MeO

Table S6 Selected bond lengths of CuIILAPIP-MeO

Number Atom1 Atom2 Length

1 Cu1 N1 1963(2)

2 Cu1 N2 1911(2)

3 Cu1 N3 1919(2)

4 Cu1 O1 1902(2)

5 N1 C5 1333(3)

6 N1 C1 1339(4)

7 N2 C6 1429(4)

8 N2 C7 1368(3)

9 N3 C14 1423(3)

10 N3 C13 1293(3)

11 O1 C19 1320(3)

12 C4 C5 1379(4)

13 C4 C3 1367(5)

14 C4 H4 088(3)

15 C5 C6 1508(4)

16 C6 H6 109(2)

17 C6 O2 1451(3)

18 C1 C2 1368(4)

19 C1 H1 091(3)

20 C2 C3 1366(5)

CuIILAPIP-MeO

Empirical formula C28 H33 Cu N3 O2

Formula weight 50712

Crystal system Orthorhombic

Space group Pbca

a (Aring) 158660(8)

b (Aring) 145267(7)

c (Aring) 220264(11)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 507666

Z 8

T (K) 296

ρcalcd (gcm3) 1327

μ (mmndash1) 0890

Significant reflections 6328

R[I gt 25 (I)] 00470

Rw[I gt 25 (I)] 01261

Goodness of fit 0997

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S8

Figure S6 13 C NMR of NiLAPIP-OH

Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH

BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]

4877 4878 4879 4880 4881 4882 4883 4884 4885 4886

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4881843

S9

Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)

(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to

amide)

S10

Figure S9 EPR silent spectrum of NiIILAPIP

Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are

set at 50 probability

-100000

-80000

-60000

-40000

-20000

0

20000

40000

60000

80000

100000

2500 3000 3500 4000 4500

S11

Figure S11 1H NMR of NiIILAPIP-MeO

Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP

BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]

4706 4708 4710 4712 4714 4716 4718

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4711808

S12

Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca

compound E121 V E12

2 V

CuIILAPIP +041 -166

NiIILAPIP +051 -181

ZnIILIPIPOAc +027 -147

aPeak to peak difference for the Fc+ Fc couple at 298 K is 012

Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan

rate 200 mV s CH2Cl2 298 K

Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca

compound V112E V2

12E

CuIILIPIP +021 -160

NiIILIPIP +032

-189

-25 -2 -15 -1 -05 0 05 1

S13

X-Ray Crystallography data of Copper Zinc and nickel complexes

Table S1 Crystallographic data for CuIILAPIP

CuIILAPIP

Empirical formula C27 H29 Cu N3 O2

Formula weight 49109

Crystal system Monoclinic

Space group P1 21c 1

a (Aring) 95598(5)

b (Aring) 182903(9)

c (Aring) 141699(8)

α (deg) 90

β (deg) 107231(2)

γ (deg) 90

V (Aring3) 23664(2)

Z 4

T (K) 150(2)

ρcalcd (gcm3) 1378

μ (mmndash1) 0952

Reflections collected 57791

Significant reflections 9306

R[I gt 25 (I)] 00450

Rw[I gt 25 (I)] 00999

Goodness of fit 07317

Table S2 Selected bond lengths of CuIILAPIP

Bond LAPIPCuII

Cu(1)-N(2) 1955 (1958)

Cu(1)-N(3) 1955 (1972)

Cu(1)-N(4) 1921 (1924)

Cu(1)-O(5) 1901 (1895)

C(17)-O(5) 1322 (1326)

C(22)-N(4) 1414 (1412)

C(23)-N(4) 1284 (1297)

C(6)-N(2) 1400 (1400)

C(6)-O(2) 1230 (1230)

S14

Table S3 Crystallographic data for CuIILIPIP

Table S4 Selected bond lengths of CuIILIPIP

Number Atom1 Atom2 Length

1 Cu1 N1 1965

2 Cu1 O1 1912

3 Cu1 N2 1903

4 Cu1 N3 1928

5 H1 C1 101

6 N1 C1 1343

7 N1 C5 1322

8 O1 C19 1331

9 C1 C2 1372

10 C2 H2 082

11 C2 C3 137

12 N2 C7 1366

13 N2 C6 144

14 C3 H3 085

15 C3 C4 1385

16 N3 C13 1298

17 N3 C14 1417

18 C4 H4 0995

LIPIPCuII

Empirical formula C29 H33 Cu N4 O

Formula weight 51714

Crystal system Orthorhombic

Space group Pnma

a (Aring) 24983(3)

b (Aring) 69452(7)

c (Aring) 163797(17)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 28421

Z 4

T (K) 296

ρcalcd (gcm3) 1209

μ (mmndash1) 0794

Significant reflections 6328

R[I gt 25 (I)] 00561

Rw[I gt 25 (I)] 01637

Goodness of fit 0997

S15

Table S5 Crystallographic data for CuIILAPIP-MeO

Table S6 Selected bond lengths of CuIILAPIP-MeO

Number Atom1 Atom2 Length

1 Cu1 N1 1963(2)

2 Cu1 N2 1911(2)

3 Cu1 N3 1919(2)

4 Cu1 O1 1902(2)

5 N1 C5 1333(3)

6 N1 C1 1339(4)

7 N2 C6 1429(4)

8 N2 C7 1368(3)

9 N3 C14 1423(3)

10 N3 C13 1293(3)

11 O1 C19 1320(3)

12 C4 C5 1379(4)

13 C4 C3 1367(5)

14 C4 H4 088(3)

15 C5 C6 1508(4)

16 C6 H6 109(2)

17 C6 O2 1451(3)

18 C1 C2 1368(4)

19 C1 H1 091(3)

20 C2 C3 1366(5)

CuIILAPIP-MeO

Empirical formula C28 H33 Cu N3 O2

Formula weight 50712

Crystal system Orthorhombic

Space group Pbca

a (Aring) 158660(8)

b (Aring) 145267(7)

c (Aring) 220264(11)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 507666

Z 8

T (K) 296

ρcalcd (gcm3) 1327

μ (mmndash1) 0890

Significant reflections 6328

R[I gt 25 (I)] 00470

Rw[I gt 25 (I)] 01261

Goodness of fit 0997

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S9

Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)

(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to

amide)

S10

Figure S9 EPR silent spectrum of NiIILAPIP

Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are

set at 50 probability

-100000

-80000

-60000

-40000

-20000

0

20000

40000

60000

80000

100000

2500 3000 3500 4000 4500

S11

Figure S11 1H NMR of NiIILAPIP-MeO

Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP

BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]

4706 4708 4710 4712 4714 4716 4718

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4711808

S12

Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca

compound E121 V E12

2 V

CuIILAPIP +041 -166

NiIILAPIP +051 -181

ZnIILIPIPOAc +027 -147

aPeak to peak difference for the Fc+ Fc couple at 298 K is 012

Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan

rate 200 mV s CH2Cl2 298 K

Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca

compound V112E V2

12E

CuIILIPIP +021 -160

NiIILIPIP +032

-189

-25 -2 -15 -1 -05 0 05 1

S13

X-Ray Crystallography data of Copper Zinc and nickel complexes

Table S1 Crystallographic data for CuIILAPIP

CuIILAPIP

Empirical formula C27 H29 Cu N3 O2

Formula weight 49109

Crystal system Monoclinic

Space group P1 21c 1

a (Aring) 95598(5)

b (Aring) 182903(9)

c (Aring) 141699(8)

α (deg) 90

β (deg) 107231(2)

γ (deg) 90

V (Aring3) 23664(2)

Z 4

T (K) 150(2)

ρcalcd (gcm3) 1378

μ (mmndash1) 0952

Reflections collected 57791

Significant reflections 9306

R[I gt 25 (I)] 00450

Rw[I gt 25 (I)] 00999

Goodness of fit 07317

Table S2 Selected bond lengths of CuIILAPIP

Bond LAPIPCuII

Cu(1)-N(2) 1955 (1958)

Cu(1)-N(3) 1955 (1972)

Cu(1)-N(4) 1921 (1924)

Cu(1)-O(5) 1901 (1895)

C(17)-O(5) 1322 (1326)

C(22)-N(4) 1414 (1412)

C(23)-N(4) 1284 (1297)

C(6)-N(2) 1400 (1400)

C(6)-O(2) 1230 (1230)

S14

Table S3 Crystallographic data for CuIILIPIP

Table S4 Selected bond lengths of CuIILIPIP

Number Atom1 Atom2 Length

1 Cu1 N1 1965

2 Cu1 O1 1912

3 Cu1 N2 1903

4 Cu1 N3 1928

5 H1 C1 101

6 N1 C1 1343

7 N1 C5 1322

8 O1 C19 1331

9 C1 C2 1372

10 C2 H2 082

11 C2 C3 137

12 N2 C7 1366

13 N2 C6 144

14 C3 H3 085

15 C3 C4 1385

16 N3 C13 1298

17 N3 C14 1417

18 C4 H4 0995

LIPIPCuII

Empirical formula C29 H33 Cu N4 O

Formula weight 51714

Crystal system Orthorhombic

Space group Pnma

a (Aring) 24983(3)

b (Aring) 69452(7)

c (Aring) 163797(17)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 28421

Z 4

T (K) 296

ρcalcd (gcm3) 1209

μ (mmndash1) 0794

Significant reflections 6328

R[I gt 25 (I)] 00561

Rw[I gt 25 (I)] 01637

Goodness of fit 0997

S15

Table S5 Crystallographic data for CuIILAPIP-MeO

Table S6 Selected bond lengths of CuIILAPIP-MeO

Number Atom1 Atom2 Length

1 Cu1 N1 1963(2)

2 Cu1 N2 1911(2)

3 Cu1 N3 1919(2)

4 Cu1 O1 1902(2)

5 N1 C5 1333(3)

6 N1 C1 1339(4)

7 N2 C6 1429(4)

8 N2 C7 1368(3)

9 N3 C14 1423(3)

10 N3 C13 1293(3)

11 O1 C19 1320(3)

12 C4 C5 1379(4)

13 C4 C3 1367(5)

14 C4 H4 088(3)

15 C5 C6 1508(4)

16 C6 H6 109(2)

17 C6 O2 1451(3)

18 C1 C2 1368(4)

19 C1 H1 091(3)

20 C2 C3 1366(5)

CuIILAPIP-MeO

Empirical formula C28 H33 Cu N3 O2

Formula weight 50712

Crystal system Orthorhombic

Space group Pbca

a (Aring) 158660(8)

b (Aring) 145267(7)

c (Aring) 220264(11)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 507666

Z 8

T (K) 296

ρcalcd (gcm3) 1327

μ (mmndash1) 0890

Significant reflections 6328

R[I gt 25 (I)] 00470

Rw[I gt 25 (I)] 01261

Goodness of fit 0997

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S10

Figure S9 EPR silent spectrum of NiIILAPIP

Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are

set at 50 probability

-100000

-80000

-60000

-40000

-20000

0

20000

40000

60000

80000

100000

2500 3000 3500 4000 4500

S11

Figure S11 1H NMR of NiIILAPIP-MeO

Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP

BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]

4706 4708 4710 4712 4714 4716 4718

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4711808

S12

Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca

compound E121 V E12

2 V

CuIILAPIP +041 -166

NiIILAPIP +051 -181

ZnIILIPIPOAc +027 -147

aPeak to peak difference for the Fc+ Fc couple at 298 K is 012

Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan

rate 200 mV s CH2Cl2 298 K

Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca

compound V112E V2

12E

CuIILIPIP +021 -160

NiIILIPIP +032

-189

-25 -2 -15 -1 -05 0 05 1

S13

X-Ray Crystallography data of Copper Zinc and nickel complexes

Table S1 Crystallographic data for CuIILAPIP

CuIILAPIP

Empirical formula C27 H29 Cu N3 O2

Formula weight 49109

Crystal system Monoclinic

Space group P1 21c 1

a (Aring) 95598(5)

b (Aring) 182903(9)

c (Aring) 141699(8)

α (deg) 90

β (deg) 107231(2)

γ (deg) 90

V (Aring3) 23664(2)

Z 4

T (K) 150(2)

ρcalcd (gcm3) 1378

μ (mmndash1) 0952

Reflections collected 57791

Significant reflections 9306

R[I gt 25 (I)] 00450

Rw[I gt 25 (I)] 00999

Goodness of fit 07317

Table S2 Selected bond lengths of CuIILAPIP

Bond LAPIPCuII

Cu(1)-N(2) 1955 (1958)

Cu(1)-N(3) 1955 (1972)

Cu(1)-N(4) 1921 (1924)

Cu(1)-O(5) 1901 (1895)

C(17)-O(5) 1322 (1326)

C(22)-N(4) 1414 (1412)

C(23)-N(4) 1284 (1297)

C(6)-N(2) 1400 (1400)

C(6)-O(2) 1230 (1230)

S14

Table S3 Crystallographic data for CuIILIPIP

Table S4 Selected bond lengths of CuIILIPIP

Number Atom1 Atom2 Length

1 Cu1 N1 1965

2 Cu1 O1 1912

3 Cu1 N2 1903

4 Cu1 N3 1928

5 H1 C1 101

6 N1 C1 1343

7 N1 C5 1322

8 O1 C19 1331

9 C1 C2 1372

10 C2 H2 082

11 C2 C3 137

12 N2 C7 1366

13 N2 C6 144

14 C3 H3 085

15 C3 C4 1385

16 N3 C13 1298

17 N3 C14 1417

18 C4 H4 0995

LIPIPCuII

Empirical formula C29 H33 Cu N4 O

Formula weight 51714

Crystal system Orthorhombic

Space group Pnma

a (Aring) 24983(3)

b (Aring) 69452(7)

c (Aring) 163797(17)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 28421

Z 4

T (K) 296

ρcalcd (gcm3) 1209

μ (mmndash1) 0794

Significant reflections 6328

R[I gt 25 (I)] 00561

Rw[I gt 25 (I)] 01637

Goodness of fit 0997

S15

Table S5 Crystallographic data for CuIILAPIP-MeO

Table S6 Selected bond lengths of CuIILAPIP-MeO

Number Atom1 Atom2 Length

1 Cu1 N1 1963(2)

2 Cu1 N2 1911(2)

3 Cu1 N3 1919(2)

4 Cu1 O1 1902(2)

5 N1 C5 1333(3)

6 N1 C1 1339(4)

7 N2 C6 1429(4)

8 N2 C7 1368(3)

9 N3 C14 1423(3)

10 N3 C13 1293(3)

11 O1 C19 1320(3)

12 C4 C5 1379(4)

13 C4 C3 1367(5)

14 C4 H4 088(3)

15 C5 C6 1508(4)

16 C6 H6 109(2)

17 C6 O2 1451(3)

18 C1 C2 1368(4)

19 C1 H1 091(3)

20 C2 C3 1366(5)

CuIILAPIP-MeO

Empirical formula C28 H33 Cu N3 O2

Formula weight 50712

Crystal system Orthorhombic

Space group Pbca

a (Aring) 158660(8)

b (Aring) 145267(7)

c (Aring) 220264(11)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 507666

Z 8

T (K) 296

ρcalcd (gcm3) 1327

μ (mmndash1) 0890

Significant reflections 6328

R[I gt 25 (I)] 00470

Rw[I gt 25 (I)] 01261

Goodness of fit 0997

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S11

Figure S11 1H NMR of NiIILAPIP-MeO

Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP

BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]

4706 4708 4710 4712 4714 4716 4718

mz

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

4711808

S12

Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca

compound E121 V E12

2 V

CuIILAPIP +041 -166

NiIILAPIP +051 -181

ZnIILIPIPOAc +027 -147

aPeak to peak difference for the Fc+ Fc couple at 298 K is 012

Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan

rate 200 mV s CH2Cl2 298 K

Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca

compound V112E V2

12E

CuIILIPIP +021 -160

NiIILIPIP +032

-189

-25 -2 -15 -1 -05 0 05 1

S13

X-Ray Crystallography data of Copper Zinc and nickel complexes

Table S1 Crystallographic data for CuIILAPIP

CuIILAPIP

Empirical formula C27 H29 Cu N3 O2

Formula weight 49109

Crystal system Monoclinic

Space group P1 21c 1

a (Aring) 95598(5)

b (Aring) 182903(9)

c (Aring) 141699(8)

α (deg) 90

β (deg) 107231(2)

γ (deg) 90

V (Aring3) 23664(2)

Z 4

T (K) 150(2)

ρcalcd (gcm3) 1378

μ (mmndash1) 0952

Reflections collected 57791

Significant reflections 9306

R[I gt 25 (I)] 00450

Rw[I gt 25 (I)] 00999

Goodness of fit 07317

Table S2 Selected bond lengths of CuIILAPIP

Bond LAPIPCuII

Cu(1)-N(2) 1955 (1958)

Cu(1)-N(3) 1955 (1972)

Cu(1)-N(4) 1921 (1924)

Cu(1)-O(5) 1901 (1895)

C(17)-O(5) 1322 (1326)

C(22)-N(4) 1414 (1412)

C(23)-N(4) 1284 (1297)

C(6)-N(2) 1400 (1400)

C(6)-O(2) 1230 (1230)

S14

Table S3 Crystallographic data for CuIILIPIP

Table S4 Selected bond lengths of CuIILIPIP

Number Atom1 Atom2 Length

1 Cu1 N1 1965

2 Cu1 O1 1912

3 Cu1 N2 1903

4 Cu1 N3 1928

5 H1 C1 101

6 N1 C1 1343

7 N1 C5 1322

8 O1 C19 1331

9 C1 C2 1372

10 C2 H2 082

11 C2 C3 137

12 N2 C7 1366

13 N2 C6 144

14 C3 H3 085

15 C3 C4 1385

16 N3 C13 1298

17 N3 C14 1417

18 C4 H4 0995

LIPIPCuII

Empirical formula C29 H33 Cu N4 O

Formula weight 51714

Crystal system Orthorhombic

Space group Pnma

a (Aring) 24983(3)

b (Aring) 69452(7)

c (Aring) 163797(17)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 28421

Z 4

T (K) 296

ρcalcd (gcm3) 1209

μ (mmndash1) 0794

Significant reflections 6328

R[I gt 25 (I)] 00561

Rw[I gt 25 (I)] 01637

Goodness of fit 0997

S15

Table S5 Crystallographic data for CuIILAPIP-MeO

Table S6 Selected bond lengths of CuIILAPIP-MeO

Number Atom1 Atom2 Length

1 Cu1 N1 1963(2)

2 Cu1 N2 1911(2)

3 Cu1 N3 1919(2)

4 Cu1 O1 1902(2)

5 N1 C5 1333(3)

6 N1 C1 1339(4)

7 N2 C6 1429(4)

8 N2 C7 1368(3)

9 N3 C14 1423(3)

10 N3 C13 1293(3)

11 O1 C19 1320(3)

12 C4 C5 1379(4)

13 C4 C3 1367(5)

14 C4 H4 088(3)

15 C5 C6 1508(4)

16 C6 H6 109(2)

17 C6 O2 1451(3)

18 C1 C2 1368(4)

19 C1 H1 091(3)

20 C2 C3 1366(5)

CuIILAPIP-MeO

Empirical formula C28 H33 Cu N3 O2

Formula weight 50712

Crystal system Orthorhombic

Space group Pbca

a (Aring) 158660(8)

b (Aring) 145267(7)

c (Aring) 220264(11)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 507666

Z 8

T (K) 296

ρcalcd (gcm3) 1327

μ (mmndash1) 0890

Significant reflections 6328

R[I gt 25 (I)] 00470

Rw[I gt 25 (I)] 01261

Goodness of fit 0997

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S12

Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca

compound E121 V E12

2 V

CuIILAPIP +041 -166

NiIILAPIP +051 -181

ZnIILIPIPOAc +027 -147

aPeak to peak difference for the Fc+ Fc couple at 298 K is 012

Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan

rate 200 mV s CH2Cl2 298 K

Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca

compound V112E V2

12E

CuIILIPIP +021 -160

NiIILIPIP +032

-189

-25 -2 -15 -1 -05 0 05 1

S13

X-Ray Crystallography data of Copper Zinc and nickel complexes

Table S1 Crystallographic data for CuIILAPIP

CuIILAPIP

Empirical formula C27 H29 Cu N3 O2

Formula weight 49109

Crystal system Monoclinic

Space group P1 21c 1

a (Aring) 95598(5)

b (Aring) 182903(9)

c (Aring) 141699(8)

α (deg) 90

β (deg) 107231(2)

γ (deg) 90

V (Aring3) 23664(2)

Z 4

T (K) 150(2)

ρcalcd (gcm3) 1378

μ (mmndash1) 0952

Reflections collected 57791

Significant reflections 9306

R[I gt 25 (I)] 00450

Rw[I gt 25 (I)] 00999

Goodness of fit 07317

Table S2 Selected bond lengths of CuIILAPIP

Bond LAPIPCuII

Cu(1)-N(2) 1955 (1958)

Cu(1)-N(3) 1955 (1972)

Cu(1)-N(4) 1921 (1924)

Cu(1)-O(5) 1901 (1895)

C(17)-O(5) 1322 (1326)

C(22)-N(4) 1414 (1412)

C(23)-N(4) 1284 (1297)

C(6)-N(2) 1400 (1400)

C(6)-O(2) 1230 (1230)

S14

Table S3 Crystallographic data for CuIILIPIP

Table S4 Selected bond lengths of CuIILIPIP

Number Atom1 Atom2 Length

1 Cu1 N1 1965

2 Cu1 O1 1912

3 Cu1 N2 1903

4 Cu1 N3 1928

5 H1 C1 101

6 N1 C1 1343

7 N1 C5 1322

8 O1 C19 1331

9 C1 C2 1372

10 C2 H2 082

11 C2 C3 137

12 N2 C7 1366

13 N2 C6 144

14 C3 H3 085

15 C3 C4 1385

16 N3 C13 1298

17 N3 C14 1417

18 C4 H4 0995

LIPIPCuII

Empirical formula C29 H33 Cu N4 O

Formula weight 51714

Crystal system Orthorhombic

Space group Pnma

a (Aring) 24983(3)

b (Aring) 69452(7)

c (Aring) 163797(17)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 28421

Z 4

T (K) 296

ρcalcd (gcm3) 1209

μ (mmndash1) 0794

Significant reflections 6328

R[I gt 25 (I)] 00561

Rw[I gt 25 (I)] 01637

Goodness of fit 0997

S15

Table S5 Crystallographic data for CuIILAPIP-MeO

Table S6 Selected bond lengths of CuIILAPIP-MeO

Number Atom1 Atom2 Length

1 Cu1 N1 1963(2)

2 Cu1 N2 1911(2)

3 Cu1 N3 1919(2)

4 Cu1 O1 1902(2)

5 N1 C5 1333(3)

6 N1 C1 1339(4)

7 N2 C6 1429(4)

8 N2 C7 1368(3)

9 N3 C14 1423(3)

10 N3 C13 1293(3)

11 O1 C19 1320(3)

12 C4 C5 1379(4)

13 C4 C3 1367(5)

14 C4 H4 088(3)

15 C5 C6 1508(4)

16 C6 H6 109(2)

17 C6 O2 1451(3)

18 C1 C2 1368(4)

19 C1 H1 091(3)

20 C2 C3 1366(5)

CuIILAPIP-MeO

Empirical formula C28 H33 Cu N3 O2

Formula weight 50712

Crystal system Orthorhombic

Space group Pbca

a (Aring) 158660(8)

b (Aring) 145267(7)

c (Aring) 220264(11)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 507666

Z 8

T (K) 296

ρcalcd (gcm3) 1327

μ (mmndash1) 0890

Significant reflections 6328

R[I gt 25 (I)] 00470

Rw[I gt 25 (I)] 01261

Goodness of fit 0997

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S13

X-Ray Crystallography data of Copper Zinc and nickel complexes

Table S1 Crystallographic data for CuIILAPIP

CuIILAPIP

Empirical formula C27 H29 Cu N3 O2

Formula weight 49109

Crystal system Monoclinic

Space group P1 21c 1

a (Aring) 95598(5)

b (Aring) 182903(9)

c (Aring) 141699(8)

α (deg) 90

β (deg) 107231(2)

γ (deg) 90

V (Aring3) 23664(2)

Z 4

T (K) 150(2)

ρcalcd (gcm3) 1378

μ (mmndash1) 0952

Reflections collected 57791

Significant reflections 9306

R[I gt 25 (I)] 00450

Rw[I gt 25 (I)] 00999

Goodness of fit 07317

Table S2 Selected bond lengths of CuIILAPIP

Bond LAPIPCuII

Cu(1)-N(2) 1955 (1958)

Cu(1)-N(3) 1955 (1972)

Cu(1)-N(4) 1921 (1924)

Cu(1)-O(5) 1901 (1895)

C(17)-O(5) 1322 (1326)

C(22)-N(4) 1414 (1412)

C(23)-N(4) 1284 (1297)

C(6)-N(2) 1400 (1400)

C(6)-O(2) 1230 (1230)

S14

Table S3 Crystallographic data for CuIILIPIP

Table S4 Selected bond lengths of CuIILIPIP

Number Atom1 Atom2 Length

1 Cu1 N1 1965

2 Cu1 O1 1912

3 Cu1 N2 1903

4 Cu1 N3 1928

5 H1 C1 101

6 N1 C1 1343

7 N1 C5 1322

8 O1 C19 1331

9 C1 C2 1372

10 C2 H2 082

11 C2 C3 137

12 N2 C7 1366

13 N2 C6 144

14 C3 H3 085

15 C3 C4 1385

16 N3 C13 1298

17 N3 C14 1417

18 C4 H4 0995

LIPIPCuII

Empirical formula C29 H33 Cu N4 O

Formula weight 51714

Crystal system Orthorhombic

Space group Pnma

a (Aring) 24983(3)

b (Aring) 69452(7)

c (Aring) 163797(17)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 28421

Z 4

T (K) 296

ρcalcd (gcm3) 1209

μ (mmndash1) 0794

Significant reflections 6328

R[I gt 25 (I)] 00561

Rw[I gt 25 (I)] 01637

Goodness of fit 0997

S15

Table S5 Crystallographic data for CuIILAPIP-MeO

Table S6 Selected bond lengths of CuIILAPIP-MeO

Number Atom1 Atom2 Length

1 Cu1 N1 1963(2)

2 Cu1 N2 1911(2)

3 Cu1 N3 1919(2)

4 Cu1 O1 1902(2)

5 N1 C5 1333(3)

6 N1 C1 1339(4)

7 N2 C6 1429(4)

8 N2 C7 1368(3)

9 N3 C14 1423(3)

10 N3 C13 1293(3)

11 O1 C19 1320(3)

12 C4 C5 1379(4)

13 C4 C3 1367(5)

14 C4 H4 088(3)

15 C5 C6 1508(4)

16 C6 H6 109(2)

17 C6 O2 1451(3)

18 C1 C2 1368(4)

19 C1 H1 091(3)

20 C2 C3 1366(5)

CuIILAPIP-MeO

Empirical formula C28 H33 Cu N3 O2

Formula weight 50712

Crystal system Orthorhombic

Space group Pbca

a (Aring) 158660(8)

b (Aring) 145267(7)

c (Aring) 220264(11)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 507666

Z 8

T (K) 296

ρcalcd (gcm3) 1327

μ (mmndash1) 0890

Significant reflections 6328

R[I gt 25 (I)] 00470

Rw[I gt 25 (I)] 01261

Goodness of fit 0997

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S14

Table S3 Crystallographic data for CuIILIPIP

Table S4 Selected bond lengths of CuIILIPIP

Number Atom1 Atom2 Length

1 Cu1 N1 1965

2 Cu1 O1 1912

3 Cu1 N2 1903

4 Cu1 N3 1928

5 H1 C1 101

6 N1 C1 1343

7 N1 C5 1322

8 O1 C19 1331

9 C1 C2 1372

10 C2 H2 082

11 C2 C3 137

12 N2 C7 1366

13 N2 C6 144

14 C3 H3 085

15 C3 C4 1385

16 N3 C13 1298

17 N3 C14 1417

18 C4 H4 0995

LIPIPCuII

Empirical formula C29 H33 Cu N4 O

Formula weight 51714

Crystal system Orthorhombic

Space group Pnma

a (Aring) 24983(3)

b (Aring) 69452(7)

c (Aring) 163797(17)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 28421

Z 4

T (K) 296

ρcalcd (gcm3) 1209

μ (mmndash1) 0794

Significant reflections 6328

R[I gt 25 (I)] 00561

Rw[I gt 25 (I)] 01637

Goodness of fit 0997

S15

Table S5 Crystallographic data for CuIILAPIP-MeO

Table S6 Selected bond lengths of CuIILAPIP-MeO

Number Atom1 Atom2 Length

1 Cu1 N1 1963(2)

2 Cu1 N2 1911(2)

3 Cu1 N3 1919(2)

4 Cu1 O1 1902(2)

5 N1 C5 1333(3)

6 N1 C1 1339(4)

7 N2 C6 1429(4)

8 N2 C7 1368(3)

9 N3 C14 1423(3)

10 N3 C13 1293(3)

11 O1 C19 1320(3)

12 C4 C5 1379(4)

13 C4 C3 1367(5)

14 C4 H4 088(3)

15 C5 C6 1508(4)

16 C6 H6 109(2)

17 C6 O2 1451(3)

18 C1 C2 1368(4)

19 C1 H1 091(3)

20 C2 C3 1366(5)

CuIILAPIP-MeO

Empirical formula C28 H33 Cu N3 O2

Formula weight 50712

Crystal system Orthorhombic

Space group Pbca

a (Aring) 158660(8)

b (Aring) 145267(7)

c (Aring) 220264(11)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 507666

Z 8

T (K) 296

ρcalcd (gcm3) 1327

μ (mmndash1) 0890

Significant reflections 6328

R[I gt 25 (I)] 00470

Rw[I gt 25 (I)] 01261

Goodness of fit 0997

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S15

Table S5 Crystallographic data for CuIILAPIP-MeO

Table S6 Selected bond lengths of CuIILAPIP-MeO

Number Atom1 Atom2 Length

1 Cu1 N1 1963(2)

2 Cu1 N2 1911(2)

3 Cu1 N3 1919(2)

4 Cu1 O1 1902(2)

5 N1 C5 1333(3)

6 N1 C1 1339(4)

7 N2 C6 1429(4)

8 N2 C7 1368(3)

9 N3 C14 1423(3)

10 N3 C13 1293(3)

11 O1 C19 1320(3)

12 C4 C5 1379(4)

13 C4 C3 1367(5)

14 C4 H4 088(3)

15 C5 C6 1508(4)

16 C6 H6 109(2)

17 C6 O2 1451(3)

18 C1 C2 1368(4)

19 C1 H1 091(3)

20 C2 C3 1366(5)

CuIILAPIP-MeO

Empirical formula C28 H33 Cu N3 O2

Formula weight 50712

Crystal system Orthorhombic

Space group Pbca

a (Aring) 158660(8)

b (Aring) 145267(7)

c (Aring) 220264(11)

α (deg) 9000

β (deg) 9000

γ (deg) 9000

V (Aring3) 507666

Z 8

T (K) 296

ρcalcd (gcm3) 1327

μ (mmndash1) 0890

Significant reflections 6328

R[I gt 25 (I)] 00470

Rw[I gt 25 (I)] 01261

Goodness of fit 0997

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S16

21 C2 H2 085(3)

22 C3 H3 086(3)

23 C19 C14 1407(4)

24 C19 C18 1418(4)

25 C14 C15 1391(4)

26 C18 C17 1382(4)

27 C18 C20 1538(4)

28 C16 C15 1378(4)

29 C16 C17 1396(4)

30 C16 C24 1537(4)

31 C13 C12 1433(4)

32 C13 H13 092(3)

33 C15 H15 089(2)

34 C12 C7 1426(4)

35 C12 C11 1409(4)

36 C7 C8 1419(4)

37 C11 C10 1362(5)

38 C11 H11 089(3)

39 C17 H17 093(3)

Table S7 Crystallographic data for ZnLAPIPOAc

ZnIILAPIPOAc

Empirical formula C29 H34 N3 O350 Zn

Formula weight 54596

Temperature K 293(2)

Wavelength Aring 071073

Crystal system space group Triclinic P-1

Unit cell dimensions Aringdeg a = 101927(13)

b = 102059(12)

c = 147907(19)

alpha = 94834(10)

beta = 98779(11)

gamma = 114583(12)

Volume Aring3 13640(3)

Z Calculated density Mgm3 2 1329

Absorption coefficient mm-1 0937

Goodness-of-fit on F2 1073

Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711

R indices (all data) R1 = 00871 wR2 = 02184

Largest diff peak and hole eAring-3 0891 and -0568

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S17

Table S8 Bond lengths of ZnLIPIPOAc

Bond length

Angles

Zn1-O1 1978(3) O1-Zn1-O2 11195(14)

Zn1-O2 1991(4) O1-Zn1-N1 8173(12)

Zn1-N1 2087(3) O2-Zn1-N1 11706(15)

Zn1-N3 2109(4) O1-Zn1-N3 9671(13)

Zn1-N2 2174(3) O2-Zn1-N3 10545(15)

O1-C1 1311(5) N1-Zn1-N3 13479(14)

C1-C2 1431(5) O1-Zn1-N2 15335(14)

C1-C6 1432(5) O2-Zn1-N2 9467(13)

C2-C3 1392(5) N1-Zn1-N2 8504(13)

C2-C20 1543(5) N3-Zn1-N2 7660(13)

C3-C4 1391(6) C1-O1-Zn1 1147(2)

C4-C5 1390(6) O1-C1-C2 1230(3)

C4-C24 1546(6) O1-C1-C6 1198(3)

C5-C6 1386(5) C2-C1-C6 1171(3)

C6-N1 1426(5) C3-C2-C1 1191(3)

N1-C7 1281(5) C3-C2-C20 1213(4)

C7-C8 1471(6) C1-C2-C20 1196(3)

C8-C9 1394(6) C4-C3-C2 1235(4)

C8-C13 1428(6) C5-C4-C3 1175(4)

C9-C10 1390(6) C5-C4-C24 1215(4)

C10-C11 1364(7) C3-C4-C24 1211(4)

C11-C12 1383(7) C6-C5-C4 1218(4)

C12-C13 1394(6) C5-C6-N1 1252(4)

C13-N2 1419(5) C5-C6-C1 1211(4)

N2-C14 1249(6) N1-C6-C1 1136(3)

C14-C15 1465(6) C7-N1-C6 1235(3)

C15-N3 1354(6) C7-N1-Zn1 1262(3)

C15-C16 1374(6) C6-N1-Zn1 1101(2)

C16-C17 1389(7) N1-C7-C8 1272(4)

C17-C18 1400(8) C9-C8-C13 1168(4)

C18-C19 1380(7) C9-C8-C7 1165(4)

C19-N3 1326(6) C13-C8-C7 1267(4)

C20-C21 1528(7) C10-C9-C8 1217(4)

C20-C23 1531(7) C11-C10-C9 1209(4)

C20-C22 1552(6) C10-C11-C12 1197(4)

C24-C27 1493(9) C11-C12-C13 1206(4)

C24-C25 1502(7) C12-C13-N2 1218(4)

C24-C26 1569(8) C12-C13-C8 1204(4)

O2-C28 1209(7) N2-C13-C8 1178(4)

C28-O3 1246(7) C14-N2-C13 1216(4)

C28-C29 1528(9) C14-N2-Zn1 1143(3)

C13-N2-Zn1 1240(3)

N2-C14-C15 1189(4)

N3-C15-C16 1225(4)

N3-C15-C14 1155(4)

C16-C15-C14 1219(4)

C15-C16-C17 1186(5)

C16-C17-C18 1187(5)

C19-C18-C17 1191(5)

N3-C19-C18 1220(5)

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S18

Table S9 Crystallographic data for NiIILAPIP

Table S10 Selected bond lengths of NiIILAPIP

Atom1 Atom2 Length

Ni1 N1 1846(2)

Ni1 O1 1838(2)

Ni1 N2 1885(2)

Ni1 N3 1888(2)

N1 C13 1287(4)

N1 C14 1417(3)

O1 C19 1333(2)

C1 C2 1378(4)

C1 N2 1329(4)

C2 H2 0929(3)

C2 C3 1378(4)

O2 C6 1224(3)

N2 C5 1342(3)

C3 H3 0929(3)

C3 C4 1379(4)

N3 C6 1379(3)

N3 C7 1393(4)

C5 C6 1487(4)

C5 C4 1380(4)

C7 C8 1410(4)

C7 C12 1412(4)

NiIILAPIP

Empirical formula C27 H29 Ni N3 O2

Formula weight 48622

Crystal system Monoclinic

Space group P 21c

a (Aring) 97052(6)

b (Aring) 180704(11)

c (Aring) 141301(10)

α (deg) 90

β (deg) 1078527(15)

γ (deg) 90

V (Aring3) 235877

Z 4

T (K) 296

ρcalcd (gcm3) 1369

μ (mmndash1) 0852

R[I gt 25 (I)] 004361

Rw[I gt 25 (I)] 01353

Goodness of fit 07317

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S19

Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO

NiIILAPIP-MeO

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Crystal system Monoclinic

Space group P 21c

a (Aring) 115267(8) A

b (Aring) 166156(10) A

c (Aring) 136845(9)

α (deg) 90

β (deg) 104524(7)

γ (deg) 90

V (Aring3) 25371(3)

Z 4

T (K) 298

ρcalcd (gcm3) 1315

R[I gt 25 (I)] R1 = 00339

Rw[I gt 25 (I)] wR2 = 00869

Goodness of fit 1073

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S20

Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO

Number Atom1 Atom2 Length

1 Ni1 O1 1843(2)

2 Ni1 N1 1844(2)

3 Ni1 N2 1852(2)

4 Ni1 N3 1882(2)

5 O1 C1 1331(4)

6 C1 C2 1413(4)

7 C1 C6 1408(4)

8 C2 C3 1385(4)

9 C2 C20 1537(5)

10 C3 H3A 093

11 C3 C4 1409(4)

12 C4 C5 1386(4)

13 C4 C24 1538(4)

14 C5 H5A 093

15 C5 C6 1396(4)

16 C6 N1 1425(3)

17 N1 C7 1308(4)

19 C7 C8 1420(4)

20 C8 C9 1417(4)

21 C8 C13 1431(4)

23 C9 C10 1360(4)

25 C10 C11 1400(5)

27 C11 C12 1376(5)

29 C12 C13 1418(4)

30 C13 N2 1367(4)

31 N2 C14 1448(4)

33 C14 C15 1504(4)

34 C14 O2 1438(3)

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S21

Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO

Identification code NiIILAPIP-MeO e712a

Empirical formula C28 H33 N3 Ni O2

Formula weight 50228

Temperature 293(2) K

Wavelength 071073 Aring

Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 93643(8) Aring

b = 99780(8) Aring

c = 143688(12) Aring

α = 101276(7)deg

β = 95203(7)deg

γ = 99728(7)deg

Volume 128704(19) Aring3

Z 2

Density (calculated) 1296 Mgm3

Absorption coefficient 0783 mm-1

F(000) 532

Crystal size 0544 x 0318 x 0130 mm3

Theta range for data collection 2225 to 28096deg

Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18

Reflections collected 8310

Independent reflections 5514 [R(int) = 00542]

Completeness to theta = 25000deg 999

Absorption correction Analytical

Max and min transmission 0909 and 0725

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5514 0 307

Goodness-of-fit on F2 1028

Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246

R indices (all data) R1 = 00671 wR2 = 01377

Extinction coefficient na

Largest diff peak and hole 0408 and -0517 eAring-3

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S22

Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO

Bond Angle

Ni1-O1 18431(18) O1-Ni1-N1 8658(8)

Ni1-N1 1844(2) O1-Ni1-N2 17597(9)

Ni1-N2 1853(2) N1-Ni1-N2 9636(9)

Ni1-N3 1881(2) O1-Ni1-N3 9135(9)

O1-C1 1330(3) N1-Ni1-N3 17769(9)

C1-C6 1408(3) N2-Ni1-N3 8577(9)

C1-C2 1413(3) C1-O1-Ni1 11308(16)

C2-C3 1386(4) O1-C1-C6 1168(2)

C2-C20 1537(4) O1-C1-C2 1242(2)

C3-C4 1409(4) C6-C1-C2 1190(2)

C4-C5 1385(3) C3-C2-C1 1169(2)

C4-C24 1539(3) C3-C2-C20 1227(2)

C5-C6 1395(3) C1-C2-C20 1204(2)

C6-N1 1425(3) C2-C3-C4 1247(2)

N1-C7 1308(3) C5-C4-C3 1174(2)

C7-C8 1422(3) C5-C4-C24 1233(2)

C8-C9 1418(4) C3-C4-C24 1193(2)

C8-C13 1429(4) C4-C5-C6 1197(2)

C9-C10 1360(4) C5-C6-C1 1221(2)

C10-C11 1401(4) C5-C6-N1 1267(2)

C10-H10A 09300 C1-C6-N1 1112(2)

C11-C12 1376(4) C7-N1-C6 1219(2)

C12-C13 1418(3) C7-N1-Ni1 12588(18)

C13-N2 1367(3) C6-N1-Ni1 11219(16)

N2-C14 1448(3) N1-C7-C8 1255(2)

C14-O2 1437(3) C9-C8-C7 1165(2)

C14-C15 1505(4) C9-C8-C13 1195(2)

C15-N3 1346(3) C7-C8-C13 1239(2)

C15-C16 1381(4) C10-C9-C8 1226(3)

C16-C17 1378(5) C9-C10-C11 1179(3)

C17-C18 1389(5) C12-C11-C10 1217(3)

C18-C19 1366(4) C11-C12-C13 1217(3)

C19-N3 1349(4) N2-C13-C12 1228(2)

C20-C23 1520(5) N2-C13-C8 1207(2)

C20-C21 1530(4) C12-C13-C8 1165(2)

C20-C22 1534(5) C13-N2-C14 1170(2)

C24-C27 1521(4) C13-N2-Ni1 12727(18)

C24-C26 1524(4) C14-N2-Ni1 11536(18)

C24-C25 1529(4) O2-C14-N2 1150(2)

O2-C28 1405(4) O2-C14-C15 1092(2)

N2-C14-C15 1088(2)

N3-C15-C16 1219(3)

N3-C15-C14 1149(2)

C16-C15-C14 1231(3)

C17-C16-C15 1194(3)

C16-C17-C18 1187(3)

C19-C18-C17 1191(3)

N3-C19-C18 1226(3)

C15-N3-C19 1183(3)

C15-N3-Ni1 11497(19)

C19-N3-Ni1 1268(2)

C23-C20-C21 1079(3)

C23-C20-C22 1094(3)

C21-C20-C22 1084(3)

S23

S23