1. Experimental Section · FT-IR spectrometer with the software of IRDM 1700. UV/Vis spectra were...

1

Electronic Supporting Information (ESI)

Void and filled supramolecular nanoprisms - Notable differences

between seemingly identical construction principles

Michael Schmittel,* Bice He

Center for Micro- and Nanochemistry and Engineering, Organische Chemie I, Universität Siegen, Adolf-Reichwein-Strasse, D-57068 Siegen, Germany,

1.1 General

All reagents were commercially available and used without further purification. Purifi-

cation and drying of the used solvents was performed according to standard methods.

Thin-layer chromatography was performed using thin-layer chromatography plates

(Silica Gel 60 F254, Merck). Silica Gel 60 was used for column chromatography.

Confirmation of the structures of all products was obtained by 1H-NMR and 13C-NMR

spectroscopy (Bruker AC200 and Avance AC 400 spectrometer, using the deuterated

solvent as the lock and residual solvent as the internal reference). The numbering of the

carbon atoms of the molecular formulae shown in the experimental section is used only

for the NMR assignments and is not in accordance with the IUPAC nomenclature rules.

Melting points were taken using a melting point apparatus of Dr. Tottoli (Büchi) and are

uncorrected. Electrospray mass spectra (ESI-MS) were recorded using a ThermoQuest

LCQ Deca. The purity of all compounds was checked by thin-layer chromatography on

SiO2 (silica gel 60 F254, Merck). Infrared spectra were recorded on a Perkin Elmer 1750

FT-IR spectrometer with the software of IRDM 1700. UV/Vis spectra were recorded on a

J&M Tidas II/Rev. 1 UV/visible Spectrometer. The degree of lithiation can readily be

monitored by GC, while the progress of substitution at phenanthroline is best controlled

by ESI-MS.

1. Experimental Section

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008

2

1.2 Synthesis

1.2.1 Synthesis of trisphenanthroline TP

NN

OH

N

N

HO

N

N

OH14

567

8

9 10

1112

13

14

TP

3-Ethynyl-2-(4-hydroxy-2,6-dimethylphenyl)-9-mesityl-[1,10]-phenanthroline 1 (500 mg,

1.13 mmol), 1,3,5-triiodobenzene (171 mg, 376 μmol) and Pd[(PPh3)4] (69.0 mg,

60.0 μmol) were dissolved in dry DMF (30 mL) and dry triethylamine (30 mL). After

deoxygenating the reaction mixture with nitrogen gas for 15 min., it was heated to 60 °C

for 4 hours. Then water (200 mL) was slowly added and the resulting precipitate was

collected by filtration. After the collected solid had been washed with 100 mL of water,

30 mL of acetone and 100 mL of dichloromethane, the crude product was purified by

recrystallisation from DMF to obtain product as yellow solid (480 mg, 343 μmol, 91%).

MP: >300 °C; IR (KBr): ν~ = 3432 (w), 3413 (w), 2918 (w), 2358 (w), 1656 (s), 1615 (s),

1588 (s), 1542 (w), 1508 (w), 1459 (s), 1390 (m), 1317 (s), 1158 (s), 1030 (w), 889 (m),

850 (s), 776 (w), 639 (w); 1H-NMR (DMF-d7, 400 MHz): δ = 2.03 (s, 18H, 10-H), 2.04

(s, 18H, 13-H), 2.31 (s, 9H, 11-H), 6.74 (s, 6H, 12-H), 6.98 (s, 6H, 9-H), 7.09 (s, 3H, 1-

H), 7.77 (d, J = 8.1 Hz, 3H, 8-H), 8.14 (d, J = 8.9 Hz, 3H, 6-H), 8.19 (d, J = 8.9 Hz, 3H,

5-H), 8.65 (d, J = 8.1 Hz, 3H, 7-H), 8.90 (s, 3H, 4-H), 9.57 (s, 3H, 14-H); 13C-NMR

(DMF-d7, 100 MHz): δ = 20.2, 20.4, 21.0, 89.6, 92.7, 114.7, 119.7, 124.5, 125.8, 126.6,

127.6, 128.1, 128.7, 128.9, 132.0, 134.4, 136.1, 137.3, 137.8, 137.9, 139.0, 140.3, 145.7,

146.4, 158.2, 160.9, 162.1; ESI-MS Calcd for [C99H78N6O3+H]+: m/z = 1399.6, Found:

m/z = 1400.0, ESI-MS Calcd for [C99H78N6O3+2H]2+: m/z = 700.3, Found: m/z = 700.5,

ESI-MS Calcd for [C99H78N6O3+3H]3+: m/z = 467.2, Found: m/z = 467.4; Anal Calcd for

C99H78N6O3•3DMF: C, 80.12; H, 6.16; N, 7.79; Found: C, 79.78; H, 6.07; N, 7.64.


3

1.2.2 Synthesis of 1-cyano-4-iododurene (B)

NC17

2 3

4

56

I

B

To a solution of 4.48 g (50.0 mmol) of cuprous cyanide in 100 mL of DMF was added

19.3 g (50.0 mmol) of 1,4-diiododurene and the resultant reaction mixture was heated at

reflux (150-160 °C) for 12 h. Subsequently, the reaction mixture was cooled to room

temperature and a solution of FeCl3 (2.00 g in 1 mL of concentrated HCl and 4 mL of

water) was added. The mixture was heated at 70-80 °C for 20 min and then extracted

with CH2Cl2. The combined extracts were washed with saturated NaCl solution, dried

over MgSO4 and the solvents removed in vacuum. The residue was subjected to column

chromatography (10% EtOAc/hexane, Rf = 0.6) to obtain 11.3 g (39.6 mmol, 79%) of 1-

cyano-4-iododurene as a white solid

MP: 179-180 °C; IR (KBr): ~ν = 2949 (w), 2216 (s), 1545 (m), 1443 (m), 1386 (m), 1258

(m), 1001 (w), 908 (m); 1H-NMR (CDCl3, 400 MHz): δ = 2.51 (s, 6H, 5-H), 2.56 (s, 6H,

6-H); 13C-NMR (CDCl3, 100 MHz): δ = 20.6, 27.6, 114.6, 117.7, 118.2, 137.4, 139.1.

1.2.3 Synthesis of 4-iodo-2,3,5,6-tetramethylbenzaldehyde (C)

I

O

17

2 3

4

56

C 1-Cyano-4-iododurene (5.70 g, 20.0 mmol) was dissolved in 50 mL of dichloromethane

at 0 °C under N2 in a 250 mL round bottom flask, then 22.0 mL of DIBAL (22.0 mmol,

1 M solution in toluene) was added slowly. The reaction mixture was allowed to attain

room temperature and stirred overnight. The reaction mixture was quenched with diluted

HCl, and the contents were heated to reflux for 30 min. Then the reaction mixture was

extracted with CH2Cl2 (2x100 mL), and the combined organic layer was dried over

MgSO4. The crude product was purified by column chromatography (SiO2, hexane:ethyl


4

acetate, 100 : 10, Rf = 0.5) to obtain product as a colourless powder in 4.49 g (15.6 mmol,

71%).

MP: 165-167 °C; IR (KBr): ~ν = 2923 (w), 2858 (w), 2742 (w), 1691 (s), 1536 (m), 1442

(w), 1382 (m), 1276 (w), 1063 (w), 918 (m), 672 (w); 1H-NMR (400 MHz, CDCl3):

δ = 2.44 (s, 6H, 5-H), 2.54 (d, J = 4.7 Hz, 6H, 6-H), 10.6 (d, J = 4.7 Hz, 1H, 7-H); 13C-

NMR (100 MHz, CDCl3): δ = 17.6, 27.6, 117.3, 134.3, 135.5, 139.0, 196.6; Anal Calcd

for C11H13IO●0.25H2O: C, 45.15; H, 4.65; Found: C, 45.19; H, 4.27.

1.2.4 Synthesis of 4-(4-iododuryl)-2,2’,6’,2”-terpyridine (D)2

I

NN N

ab

cd

e

f

g

D

Compound C (4.00 g, 13.9 mmol) was dissolved in a solution of NaOH (10.0 g,

250 mmol) in MeOH (500 mL). After stirring for 5 min at room temperature, 2-acetyl-

pyridine (6.06 g, 5.61 ml, 50.0 mmol) was added and the mixture was stirred for 1 h. The

volume of reaction mixture was reduced to about 150 mL, then water (200 mL) was

added and the mixture was extracted with CH2Cl2 (3×100 mL). The organic layers were

dried over MgSO4 and concentrated in vacuum. The solid residue and ammonium acetate

(30.0 g, 390 mmol) were dissolved in EtOH (200 ml) and heated to reflux overnight. The

solution was then cooled, reduced in volume, and water (100 mL) was added. The

mixture was extracted with CH2Cl2 (3×100 ml), and the organic layers were dried over

MgSO4 and concentrated in vacuum. Purification by column chromatography (Al2O3,

CH2Cl2, Rf = 0.9) gave 2.90 g of 4-(4-iododuryl)-2,2’,6’,2”-terpyridine (5.90 mmol, 42%)

as a yellow solid.

MP: 240-242 °C; IR (KBr): ~ν = 3048 (w), 2923 (w), 2920 (w), 2360 (w), 1605 (w), 1584

(s), 1566 (m), 1541 (m), 1465 (s), 1391 (s), 1264 (w), 1214 (w), 1116 (w), 989 (w), 902

(m), 788 (s), 731 (s), 659 (m), 622 (w); 1H-NMR (CDCl3, 400 MHz): δ = 2.08 (s, 6H, f-

H), 2.56 (s, 6H, g-H), 7.31-7.34 (m, 2H, b-H), 7.87 (td, J = 7.8 and 1.6 Hz, 2H, c-H), 8.29

(s, 2H, e-H), 8.66-8.68 (m, 4H, a-, d-H); 13C-NMR (CDCl3, 100 MHz): δ = 20.1, 27.8,

111.6, 121.4, 121.9, 124.0, 131.9, 137.0, 137.7, 140.2, 149.3, 152.6, 155.8, 156.2; ESI-


5

MS Calcd for [C25H22IN3+H]+: m/z 492.1, Found: m/z 492.0; Anal Calcd for

C25H22IN3●0.5H2O: C, 60.01; H, 4.63; N, 8.40; Found: C, 59.94; H, 4.46; N, 8.17.

1.2.5 Synthesis of tris-terpyridine TT

N

N N

N N

N

N

N

N

abc

d e

f

g

h

TT

Compound D (2.00g, 4.07 mmol), 1,3,5-triethynyl-2,4,6-trimethylbenzene 3 (260 mg,

1.35 mmol) and Pd[(PPh3)4] (230 mg, 200 μmol) were dissolved in dry DMF (50 mL)

and dry triethylamine (50 mL). After deoxygenating the reaction mixture with nitrogen

gas for 15 min., it was heated to 60 °C for 4 hours. Then water (200 mL) was added, and

the mixture was extracted twice with dichloromethane (2x100 mL). The organic layers

were combined and dried over MgSO4. After removal of the solvents, the residue was

purified first by column chromatography on aluminium oxide (CH2Cl2, Rf = 0.5) and

second by recrystallization from chloroform to furnish a light yellow solid (1.52 g,

1.18 mmol, 87%).

MP: >300 ºC; IR (KBr): ~ν = 2920 (w), 2360 (w), 2343 (w), 1604 (w), 1584 (s), 1566 (s),

1543 (m), 1467 (s), 1388 (m), 1263 (w), 1131 (w), 990 (w), 854 (w), 793 (s), 741 (m),

654 (s), 621 (w); 1H-NMR (CDCl3, 400 MHz): δ = 2.08 (s, 18H, f-H), 2.67 (s, 18H, g-H),

3.00 (s, 9H, h-H), 7.34-7.38 (m, 6H, b-H), 7.91 (td, J = 7.8 and 1.6 Hz, 6H, c-H), 8.36 (s,

6H, e-H), 8.71-8.76 (m, 12H, a-, d-H); 13C-NMR (CDCl3, 100 MHz): δ = 18.3, 19.0,

21.3, 95.1, 96.8, 121.4, 122.0, 122.4, 123.7, 123.9, 131.3, 136.2, 137.0, 140.2, 141.7,

149.3, 153.0, 155.8, 156.3; ESI-MS Calcd for [C90H75N9+H]+: m/z 1282.6, Found: m/z


6

1283.0; ESI-MS Calcd for [C90H75N9+2H]2+: m/z 641.8, Found: m/z 1642.0; Anal Calcd

for C90H75N9●0.5CHCl3: C, 80.98; H, 5.67; N, 9.39; Found: C, 80.91; H, 5.67; N, 9.02.

1.2.6 Synthesis of prism P3

N

N

N

N

OR

OR

N

N N

N N

N

N

N

N

abc

d e

1

9

10

11

12

13

4

5

6

78

f

g

h

The linear bis-phenanthroline BP1 (3.20 mg, 3.34 μmol) and Zn(CF3SO3)2 (2.43 mg,

6.68 μmol) were dissolved slowly in a mixture of dichloromethane/methanol (8.0 mL /

2.0 mL), then the mixture was heated at 40 °C for 5 minutes before a solution of tris-

terpyridine TT (2.86 mg, 2.23 μmol) in dichlorometane (10 mL) was added. After 10 ml

of acetonitrile had been added to this mixture, the mixture was stirred for 30 minutes at

room temperature. The solvents were removed. The residue was analysed by 1H-NMR, 13C-NMR, ESI-MS, and UV/Vis without further purification.

MP: >300 ºC; IR (KBr): ~ν = 2919 (w), 2361 (w), 1614 (s), 1586 (s), 1507 (w), 1458 (m),

1395 (w), 1257 (s), 1260 (s), 1032 (s), 908 (w), 850 (m), 794 (w), 640 (m); 1H-NMR

(CD3CN, 400 MHz): δ = 1.06 (s, 36H, 10-H), 1.26 (s, 54H, 11-, 13-H), 2.18 (s, 36H, g-

H), 2.22 (s, 18H, f1-H), 2.25 (s, 18H, f2-H), 2.99 (s, 18H, h-H), 6.08 (s, 12H, 9-H), 6.28

(s, 12H, 12-H), 6.54 (s, 12H, 1-H), 7.50 (t, J = 6.2 Hz, 12H, b-H), 7.84 (d, J = 6.2 Hz,

12H, a-H), 8.15 (d, J = 8.4 Hz, 6H, 8-H), 8.26 (t, J = 7.8 Hz, 12H, c-H), 8.40 (s, 12H, e-

H), 8.50 (d, J = 9.1 Hz, 6H, 6-H), 8.53 (d, J = 7.8 Hz, 12H, d-H), 8.58 (d, J = 9.1 Hz, 6H,

5-H), 9.09 (s, 6H, 4-H), 9.15 (d, J = 8.4 Hz, 6H, 7-H); 13C-NMR (CD3CN, 100 MHz):

δ = 18.6, 18.7, 18.8, 19.4, 19.5, 19.6, 20.8, 22.2, 88.5, 97.3, 97.6, 99.0, 113.9, 120.1,

122.4, 122.9, 123.3, 124.1, 124.2, 124.8, 125.6, 128.1, 128.2, 128.8, 129.0, 129.3, 130.2,

130.4, 131.6, 132.2, 132.4, 135.5, 135.8, 137.0, 137.4, 138.2, 138.7, 140.3, 140.4, 142.1,


7

142.3, 143.2, 143.4, 147.0, 148.1, 150.1, 158.5, 160.4, 161.8, 164.3; ESI-MS Calcd for

[C384H312N30O6Zn6+8OTf]4+ [M-4OTf]4+: m/z 1756.9, Found: m/z 1756.8, ESI-MS Calcd

for [C384H312N30O6Zn6+7OTf]5+ [M-5OTf]5+: m/z 1375.7, Found: m/z 1375.6, ESI-MS

Calcd for [C384H312N30O6Zn6+6OTf]6+ [M-6OTf]6+: m/z 1121.6, Found: m/z 1121.5, ESI-

MS Calcd for [C384H312N30O6Zn6+5OTf]7+ [M-7OTf]7+: m/z 940.1, Found: m/z 939.8,

ESI-MS Calcd for [C384H312N30O6Zn6+4OTf]8+ [M-8OTf]8+: m/z 803.9, Found: m/z

803.7, ESI-MS Calcd for [C384H312N30O6Zn6+3OTf]9+ [M-9OTf]9+: m/z 698.0, Found:

m/z 698.0, ESI-MS Calcd for [C384H312N30O6Zn6+2OTf]10+ [M-10OTf]10+: m/z 613.3,

Found: m/z 613.3; Anal Calcd for C396H312F36N30O42S12Zn6●8CH2Cl2: C, 58.44; H, 3.98;

N, 5.06; S, 4.63; Found: C, 58.20; H, 3.89; N, 5.29; S, 5.01.

1.2.7 Synthesis of prism P4

N

N

O

N

N

O

Fe

Fe

87

6

5

4

N

N N

N N

N

N

N

N

abc

de

1

9

10

11

12

13 f

g

h

14

151617

181920

21

22

The linear bis-phenanthroline BP2 (5.10 mg, 3.34 μmol) and Zn(CF3SO3)2 (2.43 mg,

6.68 μmol) were dissolved slowly in a mixture of dichloromethane/methanol (8.0 mL /

2.0mL). Then the mixture was heated at 40 °C for 5 minutes before a solution of tris-

terpyridine TT (2.86 mg, 2.23 μmol) in dichlorometane (10 mL) was added. After 10 ml

of acetonitrile had been added to this mixture, the mixture was stirred at room

temperature for 30 minutes. The solvents were removed, and the residue was analysed

without further purification by 1H-NMR, 13C-NMR, ESI-MS and UV/Vis.

MP: >300 ºC; IR (KBr): ~ν = 2927 (w), 2361 (w), 1603 (m), 1576 (w), 1260 (s), 1161

(m), 1031 (s), 854 (w), 796 (w), 638 (m); 1H-NMR (CD3CN, 400 MHz): δ = 1.17 (s, 36H,

10-H), 1.26(s, 54H, 11-, 13-H), 1.38 (m, 24H, 16-, 17-H), 1.52 (m, 12H, 18-H), 2.15 (s,

36H, g-H), 2.18 (s, 18H, f1-H), 2.20 (s, 18H, f2-H), 2.28 (m, 12H, 19-H), 2.79 (s, 18H, h-


8

H), 3.11 (m, 12H, 15-H), 3.59 (m, 12H, 14-H), 4.00 (m, 54H, 20-, 21-, 22-H), 5.96 (s,

12H, 9-H), 6.31 (s, 12H, 12-H), 6.88 (s, 12H, 1-H), 7.51 (t, J = 6.2 Hz, 12H, b-H), 7.80

(d, J = 6.2 Hz, 12H, a-H), 8.18 (d, J = 8.4 Hz, 6H, 8-H), 8.25 (t, J = 8.0 Hz, 12H, c-H),

8.26 (s, 12H, e-H), 8.43 (d, J = 8.0 Hz, 6H, d-H), 8.52 (d, J = 9.1 Hz, 6H, 6-H), 8.58 (d,

J = 9.1 Hz, 6H, 5-H), 9.16 (d, J = 8.4 Hz, 6H, 7-H), 9.18 (s, 6H, 4-H); 13C-NMR

(CD3CN, 100 MHz): δ = 19.0, 19.3, 19.4, 19.6, 19.8, 19.9, 21.1, 22.3, 26.7, 26.9, 30.0,

30.4, 31.5, 68.9, 69.2 (Fc), 69.6 (Fc), 70.8 (Fc), 87.6, 96.8, 97.8, 97.9, 113.4, 120.5,

123.3, 123.4, 123.7, 124.3, 124.4, 125.2, 125.9, 128.6, 129.2, 129.7, 130.0, 130.4, 130.8,

132.2, 132.4, 132.8, 135.8, 136.2, 137.7, 137.8, 138.3, 138.6, 140.8, 140.9, 142.4, 143.3,

143.6, 143.7, 144.0, 147.2, 148.3, 150.4, 160.3 160.7, 162.1, 163.6; ESI-MS Calcd for

[C480H432Fe6N30O6Zn6+7OTf]5+ [M-5OTf]5+: m/z 1697.5, Found: m/z 1697.8, ESI-MS

Calcd for [C480H432Fe6N30O6Zn6+6OTf]6+ [M-6OTf]6+: m/z 1389.8, Found: m/z 1390.0,

ESI-MS Calcd for [C480H432Fe6N30O6Zn6+5OTf]7+ [M-7OTf]7+: m/z 1169.9, Found: m/z

1170.0, ESI-MS Calcd for [C480H432Fe6N30O6Zn6+4OTf]8+ [M-8OTf]8+: m/z 1005.0,

Found: m/z 1004.7, ESI-MS Calcd for [C480H432Fe6N30O6Zn6+3OTf]9+ [M-9OTf]9+: m/z

876.8, Found: m/z 876.6, ESI-MS Calcd for [C480H432Fe6N30O6Zn6+2OTf]10+ [M-

10OTf]10+: m/z 774.2, Found: m/z 774.2; Anal Calcd for

C492H432F36Fe6N30O42S12Zn6●6CH2Cl2: C, 61.39; H, 4.59; N, 4.31; S, 3.95; Found: C,

61.03; H, 4.27; N, 4.00; S, 4.33.

Figure S1. X-ray structure of ligand TP. Three DMF solvate molecules cocrystallised with TP and are bound by hydrogen bonds.


9

Figure S2. HyperChem® structrue of prism P3. The atoms are colour coded for clarity: carbon: cyan; nitrogen: blue; oxygen: red; zinc: hidden. Left: side view; right: top view.

3.2 nm3.2 nm

0.9 nm

Figure S3. Six ferrocene units represent those in P4. They fill a periodic box of 9216 Å3 as calculated by Hyperchem®. The average distance between every two iron atoms are 2.08 nm.


10

1,4 1,6 1,8 2,0 2,2 2,4 2,6 2,8 3,0

460

465

470

475

480

485

490

495

R1

P4 L1

L2

E/m

V

Distance (nm)

Figure S4. A plot of ferrocene redox potentials vs. the average distance between ferrocene units of ferrocene containing supramolecular complexes. The supramolecular complexes R1, L1 and L2 were reported earlier.1

-2,0 -1,5 -1,0 -0,5 0,0 0,5 1,0-2,0x10-6

-1,5x10-6

-1,0x10-6

-5,0x10-7

0,0

5,0x10-7

1,0x10-6

I/A

E/V

-0,4 -0,2 0,0 0,2 0,4 0,6 0,8 1,0 1,2

0,0

2,0x10-7

4,0x10-7

6,0x10-7

8,0x10-7

1,0x10-6

I/A

E/V

Figure S5. CV (left: scan rate = 100 mV s-1) and DPV (right: step potential 2 mV) of prism P4 recorded in acetonitrile (0.10 M nBu4NPF6) using DMFc (decamethyl-ferrocene) as internal standard (E1/2 = 0). Peaks at −0.8 V, −0.9 V and −1.2 V are due to the reduction of the phenanthroline and terpyridine units, while the peak at 0.5 V corresponds to the redox potential of the ferrocene units.


11

200 250 300 350 400 4500.0

0.2

0.4

0.6

0.8

1.0

Abs

. / a

.u.

Wavelength / nm

BP1BP2TTP3P4

Figure S6. UV-Vis absorption spectra of various ligands (3.0 x 10−6 M in DCM) and complexes (1.0 x 10−6 M in acetonitrile). BP1 and BP2 display broad absorption peaks at 357 and 382 nm that can be assigned to the excitation of the phenylethynyl (p-e) units.4 The p-e absorptions in P3 and P4 are red-shifted by about 20 nm, due to the presence of the phen-Zn(II)-terpy coordination centres at the two termini of BP1 and BP2.

Figure S7. Illustration of the assumed final step of the prism assembly of P3. The atoms are colour coded for clarity: carbon: cyan; nitrogen: blue; oxygen: red; zinc: white. Left: top view; right: side view.


12

method 1

Oligomers P1, P2 P3, P4Oligomers

method 2

intermed.assembly

intermed.assembly

E

Figure S8. Graphical illustration of the final step of the prism assembly along route 1 (left) and 2 (right). Oligomers = mononuclear and oligomeric zinc(II) bisterpyridine complexes.


13

2.

94

47

3.

04

79

3.

06

77

6.

38

42

3.

20

51

2.

92

11

6.

00

80

6.

08

05

9.

00

70

36

.0

00

In

te

gr

al

9.

57

16

8.

90

56

8.

66

26

8.

64

18

8.

20

60

8.

18

39

8.

15

64

8.

13

42

7.

78

37

7.

76

36

7.

08

89

6.

97

81

6.

74

31

2.

31

40

2.

03

94

2.

02

66

( p p m)

1 . 02 . 03 . 04 . 05 . 06 . 07 . 08 . 09 . 0

* * * C u r r e n t D a t a P a r a m e t e r s * * *

N A M E :H B 0 8 0 2 3 A

E X P N O : 1

P R O C N O: 1

Figure S9.1H-NMR spectrum of ligand TP.

16

2.

10

02

16

0.

94

35

15

8.

21

88

14

6.

36

03

14

5.

74

34

14

0.

31

96

13

9.

00

01

13

7.

93

76

13

7.

84

34

13

7.

29

50

13

6.

12

12

13

4.

36

47

13

2.

05

12

12

8.

88

95

12

8.

68

39

12

8.

10

98

12

7.

56

15

12

6.

61

89

12

5.

80

50

12

4.

47

69

11

9.

76

43

11

4.

71

76

92

.6

88

5

89

.5

95

4

21

.0

06

22

0.

37

22

20

.1

83

7

( p p m)

1 02 03 04 05 06 07 08 09 01 0 01 1 01 2 01 3 01 4 01 5 01 6 0


N A M E :H B 0 8 0 2 3 A

E X P N O : 1 0

P R O C N O: 1

C 1 3 - N M R

Figure S10. 13C-NMR spectrum of ligand TP.


14

12

.0

00

5.

26

03

6.

23

89

6.

11

20

9.

10

17

18

.0

10

18

.0

13

In

te

gr

al

8.

75

76

8.

73

82

8.

73

55

8.

72

41

8.

72

21

8.

71

47

8.

71

27

8.

71

00

8.

36

35

7.

93

12

7.

92

65

7.

91

17

7.

90

77

7.

89

22

7.

88

82

7.

37

79

7.

37

53

7.

36

59

7.

36

32

7.

35

98

7.

35

71

7.

34

77

7.

34

50

2.

99

85

2.

66

68

2.

08

48

( p p m)

0 . 51 . 01 . 52 . 02 . 53 . 03 . 54 . 04 . 55 . 05 . 56 . 06 . 57 . 07 . 58 . 08 . 59 . 09 . 5


N A M E :h b 0 6 0 1 3 a

E X P N O : 1

P R O C N O: 1

h b 0 6 0 1 3 a c d c l 3

t p - p r o t o n C D C l 3 D : o c 1 3

Figure S11. 1H-NMR spectrum of ligand TT.

15

6.

34

81

15

5.

78

26

15

2.

95

50

14

9.

33

92

14

1.

70

49

14

0.

18

83

13

6.

95

80

13

6.

16

12

13

1.

29

44

12

3.

93

42

12

3.

70

29

12

2.

41

77

12

2.

00

64

12

1.

40

66

96

.8

24

29

5.

14

48

21

.3

46

21

8.

98

99

18

.3

30

2

( p p m)

1 02 03 04 05 06 07 08 09 01 0 01 1 01 2 01 3 01 4 01 5 01 6 0


N A M E :h b 0 6 0 1 3 a

E X P N O : 1 0

P R O C N O: 1

h b 0 6 0 1 3 a c d c l 3

t p - C 1 3 ( 1 h o u r ) C D C l 3 D : o c 1 3

Figure S12. 13C-NMR spectrum of ligand TT.


15

Tris-Phenol-Bis-Terpy-Zn-3#592-607 RT: 10.73-11.14 AV: 16 NL: 6.99E6T: + c Full ms [ 150.00-2000.00]

200 400 600 800 1000 1200 1400 1600 1800 2000m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

1185.1

1184.1

918.7

917.7

753.5

1628.4484.5

739.8

755.61186.9486.4

1501.9920.7429.1 1222.41173.2 1503.11463.71400.2 1985.21151.5

1675.2 1890.31226.3 1615.7947.7 1697.0891.7 1148.9 1759.3641.8426.2 487.7 1228.5

762.7 1118.5689.8573.0383.3868.9355.6

320.8259.5

1501.11501.4150 0.9

1501.8150 0.6

1501.6

1502.1

1502.61500.1

150 2.4150 2.6

1499.6

149 9.9 1503.11499.6

1503.3 150 3.6149 9.1

1499.4

1503.81504.1 150 4.31504.5

150 5.1150 5.3

1,5041,5021,5001,498

100

90

80

70

60

50

40

30

20

10

0

m/ z

1171,511 71,3

1 170,9

1171,11 171,7

1170,7

1171,9

11 72,11 170,5

1172,3

1170,31170,3

1 170,1

117 2,3

1170,1 11 72,5

1172,7

1169,9

1169,7 1173,0

1173,11173,5116 9,3

117 3,4

1169,1

1,1741,1721,1701,168

100

90

80

70

60

50

40

30

20

10

0

M4+M5+

[Zn4(TP)2(BT)2]4+

[Zn4(TP)2(BT)2]3+

[Zn4(TP)2(BT)2]5+

M4+

M5+

[Zn2(BT)]2+[Zn2(BT)2]2+

Figure S13. Top: ESI-MS spectrum of prism P1. Bottom: Theoretical (red) and experimental (black) isotopic distributions of nanoprism P1. For clarity purposes, the counter anion count was omitted in the labeling.

12

.3

32

10

.5

14

16

.2

42

16

.7

71

6.

37

83

21

.3

45

28

.5

39

14

.8

89

27

.3

42

72

.0

00

In

te

gr

al

8.

91

30

8.

81

77

8.

69

34

8.

41

68

8.

16

51

7.

92

07

7.

73

94

7.

58

63

7.

13

11

6.

35

17

6.

09

72

2.

48

52

2.

09

51

1.

87

08

1.

79

10

1.

70

70

1.

61

37

( p p m)

0 . 51 . 01 . 52 . 02 . 53 . 03 . 54 . 04 . 55 . 05 . 56 . 06 . 57 . 07 . 58 . 08 . 59 . 0


N A M E :h b 0 6 0 6 6 a

E X P N O : 1

P R O C N O: 1

h b 0 6 0 6 6 a

t p - p r o t o n 1 2 8 C D 2 C l 2 D : o c 1 6

Figure S14. 1H-NMR spectrum of prism P1 that is broadened due to rapid equilibration with oligomeric terpyridine complexes.


16

18

.8

55

40

.3

37

22

.9

11

27

.8

88

25

.6

64

23

.1

71

14

.9

07

35

.7

45

72

.0

00

In

te

gr

al

8.

76

66

8.

62

09

8.

17

04

7.

93

75

7.

90

39

7.

79

31

7.

60

51

7.

10

70

6.

71

22

6.

42

69

6.

11

06

5.

96

70

1.

81

65

1.

62

51

1.

24

91

( p p m)

- 1 . 00 . 01 . 02 . 03 . 04 . 05 . 06 . 07 . 08 . 09 . 0


N A M E :h b 0 6 0 6 5 a

E X P N O : 1

P R O C N O: 1

h b 0 6 0 6 5 a

t p - p r o t o n 1 2 8 C D 2 C l 2 D : o c 1 4

Figure S15. 1H-NMR spectrum of prism P2 that is broadened due to rapid equilibration with oligomeric terpyridine complexes..

Prism2-6#1-32 RT: 0.00-0.85 AV: 32 NL: 3.16E7T: + c ms [ 150.00-2000.00]

200 400 600 800 1000 1200 1400 1600 1800 2000m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bun

dan

ce

803.7

698.1

940.5

1121.7

1375.51122.4

613.8

1374.6359.1 699.4 805.8656.1 961.9 1144.7 1409.11366.0361.1 786.7 1021.7612.4 818.0544.1 1237.4 1516.1 1858.21756.71711.2431.9319.1 1966.5287.4

M6+

M5+

M7+

M8+

M9+

M10+

M4+M11+

Figure S16. ESI-MS spectrum of prism P3. For clarity purposes, the counter anion count was omitted in the labeling.


17

699698697

100

90

80

70

60

50

40

30

20

10

697.7697.8

698.0

698.1

697.9698.2

697.6

698.3

698.2697.4

698.3698.4697.3

698.6

698.6

697.3 698.7

698.7

698.9697.2

697.0 699.0696.9 697.1 699.4696.8

699.1 699.3699.4

696.8 699.5696.6

805804803

100

90

80

70

60

50

40

30

20

10

0

803.4

803.6803.7 803.8

804.1804.0803.5803.2

804.2 804.4

803.1

804.4803.1

802.9803.0

804.7804.6

804.9

804.8802.7

805.3805.2805.1802.6802.3

802.5802.2

939.8

940.0940.3

939.7939.6

940.1939.4

939.3940.4

939.1 940.8940.4

940.7940.6

938.9

938.8941.0

939.0

941.3941.1

938.7 941.5 941.8938.7 941.6 942.1941.7938.5

938.4942.0

942941940939

100

90

80

70

60

50

40

30

20

10

0

1.1241.1231.1221.1211.120

100

90

80

70

60

50

40

30

20

10

0

1121.0

1121.2

1121.51120.8

1121.31122.0

1121.8

1120.7 1122.1

1122.5

1120.51120.3

1122.3

1122.7

1122.81120.2

1120.0

1123.01123.71123.1 1123.3

1119.91119.7 1123.5 1123.7

1119.5

1.3781.3771.3761.3751.3741.373

100

90

80

70

60

50

40

30

20

10

0

1375.0

1376.01375.61375.2 1375.6

1375.41375.0

1374.8 1376.2

1375.81374.6

1376.2

1376.6

1374.4

1376.6

1374.4

1376.81374.0

1377.21373.8

1377.41373.81373.4 1377.8

1378.01373.2 1378.21373.6

1.7601.7581.7561.754

100

90

80

70

60

50

40

30

20

10

0

1756.51757.0

1756.3

1757.51756.0

1755.81755.5

1757.7

1757.8

1755.3

1755.1 1758.21755.0 1758.5

1758.71754.8

1759.21754.6 1759.3

1760.01759.71754.3

1754.01753.5

M5+ M6+

M7+M8+

M4+

M9+

Figure S17. Theoretical (red) and experimental (black) isotopic distributions of nano-prism P3. For clarity purposes, the counter anion count was omitted in the labeling.

6.

81

42

6.

03

28

24

.8

97

11

.8

15

15

.5

44

6.

78

26

16

.3

24

15

.3

92

9.

23

52

12

.0

00

11

.9

37

15

.1

89

14

.1

92

20

.2

40

70

.8

06

42

.9

46

35

.6

50

In

te

gr

al

9.

16

48

9.

14

33

9.

08

62

8.

59

21

8.

56

92

8.

54

17

8.

51

75

8.

49

47

8.

40

01

8.

28

73

8.

26

78

8.

25

10

8.

24

76

8.

16

71

8.

14

63

7.

87

57

7.

85

22

7.

84

01

7.

52

19

7.

50

44

7.

49

03

6.

54

57

6.

28

32

6.

07

57

2.

99

14

2.

84

50

2.

77

86

2.

25

15

2.

21

73

2.

17

97

1.

26

19

1.

06

32

( p p m)

0 . 51 . 01 . 52 . 02 . 53 . 03 . 54 . 04 . 55 . 05 . 56 . 06 . 57 . 07 . 58 . 08 . 59 . 09 . 51 0 . 0


N A M E :h b 0 6 0 1 6 b

E X P N O : 1

P R O C N O: 1

Figure S18. 1H-NMR spectrum of nanoprism P3.


18

14

3.

35

36

14

3.

23

37

14

2.

28

26

14

2.

11

98

14

0.

38

90

14

0.

27

76

13

8.

66

68

13

8.

24

69

13

7.

42

44

13

7.

03

02

13

5.

80

50

13

5.

46

22

13

2.

43

76

13

2.

22

34

13

1.

61

51

13

0.

42

41

13

0.

23

56

12

9.

33

59

12

8.

99

32

12

8.

76

18

12

8.

24

77

12

8.

16

20

12

5.

63

44

12

4.

83

76

12

4.

22

06

12

4.

18

64

12

3.

29

53

12

2.

89

26

12

2.

36

99

12

0.

10

79

11

3.

94

73

98

.9

52

89

7.

58

18

97

.2

73

4

88

.4

73

7

22

.2

32

32

0.

83

57

19

.5

76

21

9.

53

33

19

.4

47

61

8.

84

78

18

.6

50

81

8.

63

36

( p p m)

01 02 03 04 05 06 07 08 09 01 0 01 1 01 2 01 3 01 4 01 5 01 6 01 7 0


N A M E :h b 0 6 0 1 6 a

E X P N O : 1 0

P R O C N O: 1

C 1 3 - N M R

Figure S19. 13C-NMR spectrum of prism P3.

Fc-Zn-Prism-1#14-83 RT:0.31-2.13 AV:70 NL:1.85E7T:+ c ms [ 250.00-2000.00]

400 600 800 1000 1200 1400 1600 1800 2000m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

anc

e

1170.0

1390.0

1004.7

1169.1

876.6

1388.7

1696.8

877.5

774.2817.8 1697.8

924.01191.6

1429.7

1430.71155.3 1370.1 1695.4

1709.41013.1990.0655.0 1192.6 1559.61014.1 1712.3624.3 1325.7 1673.7 1860.0432.0 772.8 1731.61324.8

1863.2432.9 1954.8602.2351.1318.9

M5+

M6+

M7+

M8+

M9+

M10+

Figure S20. ESI-MS spectrum of nanoprism P4. For clarity purposes, the counter anion count was omitted in the labeling.


19

1697,2

1697,0

1697,81697,4

1696,3 1697,51698,2

1696,81696,6

1695,91696,6 1697,9

1696,4

1696,11698,0

1698,4 1699,01695,7

1695,8

1695,4 1698,61698,8

1699,0

1699,1

1699,3

1700,0

1695,3 1699,5

1699,9

1.7001.6991.6981.6971.6961.695

100

90

80

70

60

50

40

30

20

10

1389,1

1389,3 1389,4

1389,6

1389,81389,9

1389,0

1388,8

1390,3

1388,6

1390,1

1390,4

1390,61388,4

1388,31390,8

1388,11388,0

1391,11387,8 1391,4

1390,9

1391,61387,5 1391,9

1392,31387,4 1391,8

1392,1

1387,0

1.3921.3911.3901.3891.388

100

90

80

70

60

50

40

30

20

10

1169,5

1169,4

1169,7

1169,7

1169,81169,3 1169,9

1170,01169,3

1169,31169,0

1170,11169,1 1170,2

1170,4

1168,9

1170,4

1168,8

1170,81170,5

1168,81171,61168,71168,4

1168,7 1170,8

1170,91171,2 1171,5

1168,4 1171,21171,01168,1

1171,4

1168,0

1171,7

1.1721.1711.1701.1691.168

100

90

80

70

60

50

40

30

20

10

0

M5+ M6+ M7+

Figure S21. Theoretical (red) and experimental (black) isotopic distribution of prism P4. For clarity purposes, the counter anion count was omitted in the labeling.

11

.0

23

12

.6

86

11

.1

00

21

.5

05

6.

59

51

4.

40

29

10

.3

19

11

.8

82

12

.0

95

11

.1

84

11

.9

43

54

.0

00

12

.3

92

16

.1

66

12

.3

16

43

.6

18

10

0.

58

88

.0

84

12

4.

49

In

te

gr

al

9.

17

68

9.

17

21

9.

15

13

8.

60

01

8.

57

73

8.

53

23

8.

50

95

8.

43

63

8.

41

62

8.

26

38

8.

25

70

8.

23

76

8.

19

26

8.

17

18

7.

90

99

7.

80

92

7.

79

78

7.

53

13

7.

51

38

7.

50

04

6.

88

07

6.

30

80

5.

96

02

4.

00

18

3.

59

63

3.

57

75

3.

11

22

2.

88

87

2.

77

05

2.

19

58

2.

18

51

2.

17

77

2.

15

22

1.

52

71

1.

40

02

1.

36

06

1.

25

52

1.

17

40

( p p m)

0 . 51 . 01 . 52 . 02 . 53 . 03 . 54 . 04 . 55 . 05 . 56 . 06 . 57 . 07 . 58 . 08 . 59 . 09 . 51 0 . 0


N A M E :h b 0 7 0 1 1 a

E X P N O : 1

P R O C N O: 1

h b 0 7 0 1 1 a

t p - p r o t o n 1 2 8 C D 3 C N D : o c 1 1 4

Figure S22. 1H-NMR spectrum of nanoprism P4.


20

16

3.

64

62

16

2.

13

82

16

0.

72

45

16

0.

30

46

15

0.

45

11

14

8.

33

47

14

7.

22

08

14

3.

98

20

14

3.

72

50

14

3.

63

07

14

3.

32

23

14

2.

41

40

14

0.

92

31

14

0.

78

61

13

8.

60

11

13

8.

27

55

13

7.

84

71

13

7.

67

58

13

6.

15

92

13

5.

79

07

13

2.

71

47

13

2.

38

06

13

2.

23

49

13

0.

77

83

13

0.

43

56

12

9.

96

43

12

9.

73

30

12

9.

20

17

12

8.

55

91

12

5.

90

29

12

5.

24

32

12

4.

43

78

12

4.

30

07

12

3.

74

37

12

3.

40

96

12

3.

28

96

12

0.

54

78

11

3.

35

90

97

.9

27

59

7.

79

89

96

.8

22

2

87

.5

59

8

70

.8

00

37

0.

40

61

69

.5

57

96

9.

24

08

68

.8

98

16

8.

19

55

36

.7

92

73

1.

69

46

31

.6

43

23

1.

48

90

30

.4

26

53

0.

01

52

26

.8

87

82

6.

73

35

22

.2

95

22

1.

06

13

19

.8

70

31

9.

75

90

19

.5

61

91

9.

39

91

19

.2

96

31

9.

04

78

( p p m)

02 04 06 08 01 0 01 2 01 4 01 6 01 8 02 0 02 2 0


N A M E :h b 0 7 0 1 1 c

E X P N O : 1 0

P R O C N O: 1

C 1 3 - N M R

Figure S23. 13C-NMR spectrum of nanoprism P4.

1 M. Schmittel, B. He, V. Kalsani and J. W. Bats, Org. Biomol. Chem., 2007, 5, 2395–2403.

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