Page 1
Supplementary Information
Visible-light-driven Transfer Hydrogenation of Nicotinamide Cofactors with a Robust Ruthenium Complex Photocatalyst Wenjin Dong, Jie Tang, Lijun Zhao, Li Deng* and Mo Xian*
Table of Contents
Control experiments, kinetics and thermodynamics…...……..……………….………………………………...……………….………….2
Quantum yield measurements……………………………………………………………………………………….…………………………4
Synthesis of L-glutamate……………………………………………………………………………… ……………………....……......….…7
NMR spectra (Figure S8 to S50)…….……………...………………………………………………………… …………………………..…9
Electronic absorption spectra (Figure S51 to S57)………….……………….………..…….…….……………………………………..…33
Molecular structures (Figure S58 to S60)…………..……………………...………………….…..………………………….…………..…38
Mass spectra (Figure S61 to S73)…………….……………………...……………………….…..…………....……………….………...…39
References……………………………………………………………...…………………….….………………..……………….………...…44
1 / 44
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2020
Page 2
Control experiments, kinetics and thermodynamics
--BSA
ADHGSH ME
With
out 7
No irra
diatio
n0
20
40
60
80
100
120
TOF
(h-1
)
no NADH formed
Figure S1. Catalytic activities of 7 (10 uM) for transfer hydrogenation of NAD+ (1mM) in the presence of bovine serum albumin (BSA,
0.2mg mL-1), alcohol dehydrogenase (ADH, 2 U), glutathione (GSH, 1 mmol) and mercaptoethanol (ME,1 mmol) under irradiation of 40
w green LEDs (525 nm) with a fan at room temperature; reactions without 7 or irradiation can not afford NADH.
0 200 400 600 800 1000 1200
0.02
0.04
0.06
k (s
-1)
Conc. HCOONa (mM)
40 w LEDs (525 nm)50 uM Ru(tpy)(biq)Cl2
Equation y = a + b*x
Intercept 0.0193 ± 0.00206Slope 2.9898E-5 ± 3.606R-Square (COD) 0.97173
Figure S2. Rate constant (k) of the photosubstitution of 7 with formate as a function of HCOONa concentration.
(Rate constant (k) was calculated according to the results shown in Figure S51-S54)
2 / 44
Page 3
0.0031 0.0032 0.0033 0.0034 0.0035
2.8
3.0
3.2
3.4
3.6
3.8ln
(TO
F)
1/T (1/K)
T / K TOF / h-1285 20306 28322 39
Slope = -1593.31 ± 224.82R2 = 0.998
Figure S3. Relationship between TOF of NADH and temperature.
(Reaction conditions: 50 mL autoclave with a sapphire glass window on the top side and a thermocouple inside, 5 mL solution of 1mM
NAD+, 10 uM 7, 0.5 M HCOONa, irradiation of 100 w green LEDs. Note: higher or lower temperature will cause condensed water on
glass window, which affects the photo flux. )
As shown in Figure S3, apparent activation energy (Ea) was calculated according to Arrhenius equation:
Ea = −R𝑑ln(TOF)
𝑑(1T)
= 3.2 ± 0.4 kcal mol−1
Hydricity measurements were performed in sealed NMR tubes containing ca. 10 mM hydride donor at room
temperature (ca. 25 °C) and ca. 10 mM acceptor. Acetonitrile-d3 was degassed by freeze-pump-thaw cycle for
three times. Hydricity was calculated based on the thermodynamic equilibrium constant (K) according to:
DH + A AH- + D+
HydricityDH = Hydricity AH + 𝛥G = Hydricity AH − RTlnK
K = [AH] × [D][DH] × [A]
where K was estimated as 4.3 by integration of the 1H NMR spectra (Figure S44-S49), corresponding to a ΔG
of -0.9 kcal mol-1.
3 / 44
Page 4
Quantum yield measurements
The quantum yield was calculated according to:
𝜙 = mol NADH
photo flux × t × f1
where t is reaction time and f1 is the fraction of light absorbed by photocatalysts at 456 nm or 525 nm.
The photon flux of blue and green LEDs could be determined by standard ferrioxalate actinometry and
Reineckate’s salt actinomertry, respectively 1-3.
Photo flux = mol actinometry product𝜙actinometry × t × f2
where f2 is the fraction of light absorbed by ferrioxalate at 456 nm or Reineckate’s salt at 525 nm. The quantum
yield could be expressed as
𝜙 = 𝜙actinometry × rNADH × f2
ractinometry × f1
where rNADH and ractinometry are reaction rate of NADH and actinometry product, respectively. (rNADH = mol NADH
/ t, ractinometry = mol actinometry product / t)
To determine the quantum yield of NADH regeneration in the presence of photocatalyst 1 under irradiation of
40 w blue LEDs, to a 4 mL cuvette (l = 1.0 cm) was added 2 mL 0.15 M ferrioxalate aqueous sulfuric acid (0.2 M)
solution. The cuvette placed 1 cm away from 40 w blue LEDs (456 nm). After irradiation for 5 seconds, 0.1 mL
of the ferrioxalate solution was added to 0.4 mL 0.15 M 1,10-phenanthroline sulfuric acid (0.2 M) solution. After
1h, the sample was diluted to 2 mL with 0.2 M sulfuric acid solution.
0 50 100 150 200 250 300 350 400
0.0
0.2
0.4
0.6
0.8
1.0
A a
t 510
nm
Conc. Fe(II) (uM)
Equation y = a + b*x
Intercept 0.02322 ± 0.02Slope 0.00247 ± 1.67R-Square (COD) 0.98193
a)
4 / 44
Page 5
5 10 15 20 25 300
5
10
15
20
25
30
mol
of F
e(II)
(um
ol)
Time (s)
Equation y = a + b*x
Intercept 0.42782 ± 0.Slope 0.81097 ± 0.R-Square (COD) 0.99934
b)
Figure S4. a) standard curve for Fe(II) quantification; b) formation of Fe(II) under irradiation at 456 nm as a function of time.
The Fe(II) concentration of the resulting solution was measured by UV-Vis spectrometer at 510 nm. As shown
in Figure S4, the rate of Fe(II) formation (ractinometry) is 0.832 umol s-1. A solution (2 mL) of 1 mM NAD+, 0.5 M
HCOONa and 10 uM 1 was added to the same cuvette which was equipped with a rubber spetum cap and
purged with Ar through a needle. The solution was irradiated by the 40 w blue LEDs and cooled with a fan. After
15 min the NADH was measured by a UV-Vis spectrometer at 340 nm. As a result, rate of NADH formation
(rNADH) was 0.15 umol h-1. The f1 for 10 uM 1 was 0.117 (A = C1 × I × ε456 nm = 10uM × 1cm × 5368 M-1cm-1=
0.054, f = 1- 10-A =0.117). The Φactinometry and f2 for ferrioxalate were reported as 0.845 and 0.9926.2
𝜙 = 0.845 × 0.15 ÷ 3600 × 0.9926
0.832 × 0.117 = 3.6 × 10−4
Therefore quantum yield of NADH regeneration in the presence of photocatalyst 1 was 3.6×10-4.
For the quantum yield of NADH regeneration in the presence of photocatalyst 7 under irradiation of 40 w green
LEDs (525 nm), Reineckate’s salt actinomertry was applied according to a reported procedure.3 Commercially
available ammonium Reinecke’s salt was converted to the potassium salt (KCr(NH3)(SCN)4) by dissolving in
warm (40-50 °C) water, adding excess solid potassium nitrate, cooling, and filtering. The product was
recrystallized carefully two times from warm water under dimmer condtions and dried under vacuum. 2 mL of 4
mM fresh potassium Reinecke’s salt solution was added to a 4 mL cuvette. After irradiation, 0.1 mL was added
to 0.9 mL 10 mM Fe(NO3)3 nitric acid (2.5 wt %) solution. After diluted 5 times with 2.5 wt% nitric acid, the
concentration of free thiocyanate anion was determined with a UV-Vis spectrometer at 440 nm. The rate of
SCN- formation (ractinometry) was 0.119 umol s-1. The rate of NADH formation (rNADH) in the presence of 7 under
the same irradiation was 1.56 umol h-1. The f1 for 10 uM 7 was 0.117 (A = C1 × I × ε525 nm = 10uM × 1cm × 3761
M-1cm-1= 0.038, f = 1- 10-A =0.084). The Φactinometry and f2 for Reinecke’s salt were reported as 0.286 and
0.639.[5]
𝜙 = 0.286 × 1.56 ÷ 3600 × 0.639
0.119 × 0.084 = 7.9 × 10−3
Therefore quantum yield of NADH regeneration in the presence of photocatalyst 7 was 7.9×10-3.
5 / 44
Page 6
0 20 40 60 80 100 120 140 160 180
0.00
0.05
0.10
0.15
0.20
0.25
A a
t 440
nm
conc. SCN anion (uM)
Equation y = a + b*xIntercept 0.01389 ± 0.003Slope 0.00148 ± 4.885R-Square (COD) 0.99567
a)
5 10 15 200.0
0.5
1.0
1.5
2.0
2.5
mol
of S
CN
ani
on (u
mol
)
Time (s)
b)
Equation y = a + b*x
Intercept 0Slope 0.11933 ± 0.0050R-Square (COD) 0.99471
Figure S5. a) standard curve for SCN anion quantification; b) formation of SCN anion under irradiation at 525 nm as a function of time.
6 / 44
Page 7
Synthesis of L-glutamate
For L-glutamate synthesis, 4 mL 0.1M phosphate buffer (pH = 7.4) solution containing 1 mM NAD+, 50 uM
photocatalyst 7, 2 U glutamate dehydrogenase (GDH), 0.5 M HCOONa, 0.05 M (NH4)2SO4 and 10 mM
α-ketoglutarate was added to a Schlenk tube equipped with a rubber stopper and a sampling syringe and then
the tube was purged with argon and placed in front of green LEDs (100 w, 525 nm). The reaction temperature
was kept lower than 40 °C through cooling with a fan. After 1.5 h irradiation, another 10 mM α-ketoglutarate
was added and irradiated for 1 h. After a certain time irradiation, the reaction mixture was sampled and
derivated with phenyl isothiocyanate as the following procedure: To each 200 uL diluted sample was added
100uL 2.5 wt% phenyl isothiocyanate acetonitrile solution and 100 uL 1 M NEt3 acetonitrile solution. The
resulting mixture was kept at room temperature for 1 h, then 600 uL hexane was used to extract unreacted
phenyl isothiocyanate. 200 uL of bottom layer (acetonitrile) was added to 800 uL water and filtered for HPLC
analysis. Analysis of derivated L-glutamate samples was done on a Shimadzu Prominence 20 HPLC system,
equipped with a C18 column and a UV-Vis detector.
HCOO-
hv
HCO3-
NN
NRu
N
N
X
X = Cl, OH, HCOO or H
GDH OH
O
OHO
O
OH
O
NH2
HO
O
+ NH4+
NAD+
NADH
Scheme S2. Enzymatic synthesis of L-glutamate with NADH regeneration system.
0 200 400 600 800 1000 1200
0
500000
1000000
1500000
2000000
2500000
3000000
3500000
peak
are
a
concentration of L-glutamate / ppm
Equation y = a + b*x
Intercept 8299.82184 ± 3038.13Slope 2562.31905 ± 5.80121R-Square (COD) 0.99997
Figure S6. Standard curve for quantification of L-glutamate.
7 / 44
Page 8
L-glutamate (derivated)
Figure S7. HPLC chart of L-glutamate after 2.5 h irradiation.
8 / 44
Page 9
NMR spectra
-3.0-2.0-1.00.01.02.03.04.05.06.07.08.09.010.011.012.013.014.015.016.0
f1 (ppm)
-5.0E+06
0.0E+00
5.0E+06
1.0E+07
1.5E+07
2.0E+07
2.5E+07
3.0E+07
3.5E+07
4.0E+07
4.5E+07
5.0E+07
5.5E+07
Mar07-2019-0306-DL-1.1.1.1r
1.00
1.98
1.01
1.96
1.07
2.00
1.07
1.03
1.02
1.00
2.05
2.03
1.02
0.99
3.33
4.89
7.05
7.05
7.06
7.06
7.07
7.08
7.08
7.33
7.34
7.35
7.35
7.36
7.37
7.37
7.38
7.40
7.71
7.71
7.72
7.72
7.74
7.74
7.76
7.76
7.77
7.78
7.93
7.93
7.95
7.95
7.97
7.97
8.00
8.01
8.02
8.02
8.02
8.04
8.04
8.16
8.18
8.20
8.32
8.32
8.34
8.34
8.36
8.36
8.50
8.52
8.54
8.56
8.66
8.68
8.79
8.81
10.21
10.22
7.007.207.407.607.808.008.208.408.608.80.00
f1 (ppm)1.00
1.98
1.01
1.96
1.07
2.00
1.07
1.03
1.02
1.00
2.05
2.03
1.02
9.810.010.210.410.6
f1 (ppm)
Figure S8. 1H NMR (400 MHz, Methanol-d4) spectrum of complex 1.
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
-2.0E+05
0.0E+00
2.0E+05
4.0E+05
6.0E+05
8.0E+05
1.0E+06
1.2E+06
1.4E+06
1.6E+06
1.8E+06
2.0E+06
2.2E+06
2.4E+06
2.6E+06
2.8E+06
3.0E+06pdata/1
122.38
123.22
123.42
123.47
126.09
126.68
127.14
134.12
135.51
136.62
137.02
151.48
151.93
152.24
156.34
158.12
158.89
158.90
158.60158.70158.80158.90159.00159.10159.20
f1 (ppm)
0.0E+00
5.0E+05
1.0E+06
1.5E+06
158.89
158.90
Figure S9. 13C NMR (151 MHz, Methanol-d4) spectrum of complex 1.
9 / 44
Page 10
Figure S10 . 1H NMR (400 MHz, Methanol-d4) spectrum of complex 2.
Figure S11 . 13C NMR (101 MHz, Methanol-d4) spectrum of complex 2.
10 / 44
Page 11
Figure S12 . 1H NMR (400 MHz, Methanol-d4) spectrum of complex 3.
Figure S13 . 13C NMR (101 MHz, Methanol-d4) spectrum of complex 3.
11 / 44
Page 12
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.5
f1 (ppm)
Apr15-2019-ZXH-OCH3.1.fid
2.91
2.90
1.00
0.99
1.94
0.99
1.92
2.00
2.05
1.00
1.99
2.00
1.00
3.88
4.24
6.65
6.66
6.67
6.67
7.01
7.03
7.35
7.35
7.36
7.37
7.37
7.38
7.39
7.64
7.64
7.65
7.66
7.80
7.80
7.81
7.81
7.91
7.91
7.93
7.93
7.95
7.95
8.08
8.10
8.10
8.12
8.38
8.38
8.51
8.51
8.53
8.53
8.62
8.64
9.93
9.94
Figure S14 . 1H NMR (400 MHz, Methanol-d4) spectrum of complex 4.
Figure S15 . 13C NMR (101 MHz, Methanol-d4) spectrum of complex 4.
12 / 44
Page 13
Figure S16 . 1H NMR (400 MHz, Methanol-d4) spectrum of complex 5.
Figure S17 . 13C NMR (101 MHz, Methanol-d4) spectrum of complex 5.
13 / 44
Page 14
-3-2-1012345678910111213141516
f1 (ppm)
9.09
3.00
3.00
6.10
1.09
2.18
1.18
1.11
4.15
3.24
2.13
3.18
6.73
6.74
7.32
7.34
7.35
7.42
7.44
7.46
7.72
7.74
7.90
7.92
7.94
7.97
7.98
8.07
8.09
8.12
8.14
8.34
8.36
8.40
8.42
8.44
8.46
Figure S18 . 1H NMR (400 MHz, D2O) spectrum of complex 6.
Figure/Scheme S19 . 13C NMR (101 MHz, D2O) spectrum of complex 6.
14 / 44
Page 15
Figure S20. 1H NMR (400 MHz, Methanol-d4) spectrum of complex 7.
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
120.
2912
0.36
122.
5412
3.45
123.
5212
6.96
128.
2312
8.33
128.
5512
9.04
129.
3413
0.37
130.
4313
0.65
135.
4213
6.32
137.
4413
8.35
151.
1015
1.76
152.
4615
8.55
158.
9515
9.28
161.
78
Figure S21. 13C NMR (101 MHz, Methanol-d4) spectrum of complex 7.
15 / 44
Page 16
Figure S22. 1H NMR (400 MHz, DMSO-d6) spectrum of complex Ru(tpy)(biq)(Cl)PF6.
105110115120125130135140145150155160165170175
f1 (ppm)
-500000
0
500000
1000000
1500000
2000000
2500000
3000000
3500000
4000000
4500000
5000000
5500000
6000000
6500000
7000000
7500000
8000000
8500000
120.
3912
0.42
122.
2912
2.52
123.
3212
6.67
127.
3112
7.81
128.
0612
8.33
128.
4112
8.75
129.
5412
9.95
129.
9913
4.88
135.
6113
7.02
137.
59
149.
9415
0.46
151.
75
157.
6915
8.09
160.
92
Figure S23. 13C NMR (101 MHz, DMSO-d6) spectrum of complex Ru(tpy)(biq)(Cl)PF6.
16 / 44
Page 17
Figure S24. 1H NMR (400 MHz, MeCN-d3) spectrum of complex Ru(tpy)(biq)(MeCN)(PF6)2.
Figure S25. 13C NMR (101 MHz, MeCN-d3) spectrum of complex Ru(tpy)(biq)(MeCN)(PF6)2.
17 / 44
Page 18
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.513.0
f1 (ppm)
Jun-18-2019-DL-0618-1
Jun-18-2019-DL-0618-1
1.01
0.99
0.98
3.87
1.81
0.92
1.29
1.05
4.75
6.96
2.01
1.95
3.15
1.05
1.96
1.96
1.90
3.06
1.09
0.99
1.08
1.07
1.02
1.09
0.99
3.33
4.88
6.93
6.95
7.23
7.25
7.27
7.30
7.32
7.34
7.37
7.46
7.47
7.49
7.81
7.83
7.84
7.85
7.85
7.86
7.87
7.89
7.91
7.94
7.94
7.96
7.96
7.98
7.98
8.25
8.26
8.27
8.29
8.29
8.34
8.36
8.48
8.50
8.67
8.69
8.73
8.75
8.84
8.87
8.94
8.96
9.03
9.06
7.07.58.08.59.09.5
f1 (ppm)
Jun-18-2019-DL-0618-1
Jun-18-2019-DL-0618-1
Figure S26. 1H NMR (400 MHz, MeOH-d4) spectrum of complex Ru(tpy)(biq)(HCOO)PF6.
6.76.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.09.19.2.3
f1 (ppm)
-200
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
A (d)
9.05
B (d)
8.95
C (d)
8.85
D (d)
8.74
E (d)
8.68
F (m)
8.50
G (dd)
8.35
H (dt)
8.27
I (td)7.96
J (m)7.85
K (ddd)7.47
L (m)7.32
M (t)7.25
N (d)
6.94
0.99
0.94
1.86
1.07
5.69
2.13
2.07
1.09
2.24
2.07
1.06
0.95
1.11
1.00
6.93
6.95
7.25
7.30
7.32
7.34
7.47
7.47
7.81
7.83
7.83
7.84
7.85
7.85
7.86
7.86
7.86
7.87
7.88
7.89
7.89
7.89
7.94
7.94
7.96
7.96
7.98
7.98
8.25
8.26
8.27
8.28
8.29
8.34
8.34
8.36
8.36
8.48
8.48
8.50
8.50
8.51
8.67
8.69
8.73
8.75
8.84
8.86
8.94
8.96
9.03
9.06
Figure S27. 1H NMR (101 MHz, MeOH-d4) spectrum of complex Ru(tpy)(biq)(DCOO)PF6.
18 / 44
Page 19
6.36.46.56.66.76.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.09.19.29.3
f1 (ppm)
-100
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
6.64
6.66
7.07
7.09
7.10
7.12
7.14
7.23
7.25
7.26
7.52
7.54
7.59
7.60
7.76
7.79
7.80
7.82
7.84
7.97
8.00
8.15
8.17
8.19
8.25
8.27
8.28
8.35
8.37
8.46
8.48
8.53
8.55
8.72
8.74
8.79
8.81
Figure S28. 1H NMR (400 MHz, D2O) spectrum of complex [Ru(tpy)(biq)(OH)]+.
-17-16-15-14-13-12-11-10-9-8-7-6-5-4-3-2-101234567891011123
f1 (ppm)
-200
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
3200
3400
3600
Jun-11-2019-DL-0611-2/14
A (d)
9.80
B (d)
6.74
C (d)
8.87
D (d)
8.72
E (d)
8.46
F (d)
8.35
G (t)7.99
I (t)7.45
K (m)7.79
L (t)7.05
J (t)7.17
M (s)
-14.71
N (d)
8.68
O (m)
8.26
P (d)7.58
0.83
0.91
1.66
0.86
0.94
2.59
5.97
1.01
3.07
0.97
2.09
1.01
0.97
1.00
1.00
-14.
716.
736.
757.
037.
057.
077.
157.
177.
197.
437.
457.
477.
577.
587.
737.
757.
787.
797.
817.
827.
847.
977.
998.
018.
238.
248.
258.
268.
268.
268.
288.
288.
288.
348.
368.
458.
478.
678.
698.
718.
748.
868.
889.
799.
81
6.57.07.58.08.59.09.510.0
f1 (ppm)
7.03
7.05
7.07
7.57
7.58
7.73
7.75
7.78
7.82
7.84
7.99
8.25
8.26
8.26
8.26
8.28
8.28
8.28
8.45
8.47
8.67
8.69
8.86
8.88
Figure S29. 1H NMR (400 MHz, MeCN-d3) spectrum of complex Ru(tpy)(biq)(H)PF6.
19 / 44
Page 20
-17-16-15-14-13-12-11-10-9-8-7-6-5-4-3-2-101234567891011123
f1 (ppm)
-2500
-2000
-1500
-1000
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
Jun05-2019-DL-0605-2/3
0.98
1.24
1.12
2.04
2.21
1.60
2.33
1.35
1.39
5.11
1.38
1.00
-14.
63
7.05
7.06
7.12
7.13
7.15
7.29
7.31
7.33
7.78
7.79
7.81
7.83
7.84
7.87
7.89
7.91
7.94
7.96
7.98
8.18
8.20
8.22
8.61
8.63
8.65
8.67
8.69
8.86
8.88
9.69
9.70
Figure S30. 1H NMR (400 MHz, DMSO-d6) spectrum of complex Ru(tpy)(bpy)(H)PF6.
Figure S31. 1H NMR (400 MHz,MeCN-d3) spectrum of complex Ru(tpy)(bpy)(MeCN)(PF6)2.
20 / 44
Page 21
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
0.0
500.0
1000.0
1500.0
2000.0
2500.0
3000.0
3500.0
4000.0
4500.0
5000.0
117.31
123.47
123.53
124.15
124.29
126.68
127.50
127.84
136.79
137.38
137.66
138.55
151.18
152.47
153.12
155.91
157.56
157.59
158.33
Figure S32. 13C NMR (101 MHz,MeCN-d3) spectrum of complex Ru(tpy)(bpy)(MeCN)(PF6)2.
Figure S33. 1H NMR (400 MHz, CDCl3) spectrum of complex Rh(Cp*)(bpy)Cl2 .
21 / 44
Page 22
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
-500000
0
500000
1000000
1500000
2000000
2500000
3000000
3500000
4000000
4500000
5000000
5500000
6000000
6500000
7000000
7500000
8000000
8500000
9000000
9.20
76.7
2
97.1
1
125.
5412
8.43
140.
85
151.
1615
4.61
Figure S34. 13C NMR (101 MHz, CDCl3) spectrum of complex Rh(Cp*)(bpy)Cl2.
-3-2-1012345678910111213141516
f1 (ppm)
0.0E+00
5.0E+06
1.0E+07
1.5E+07
2.0E+07
2.5E+07
3.0E+07
3.5E+07
4.0E+07
4.5E+07
Apr23-2019-DL-0423.1.1.1r
2.08
5.02
1.01
0.97
1.02
1.00
4.70
5.82
7.41
8.10
8.12
8.14
8.81
8.83
8.99
9.00
9.27
Figure S35. 1H NMR (400 MHz, D2O) spectrum of (BNA)Br.
22 / 44
Page 23
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
-2000000
-1000000
0
1000000
2000000
3000000
4000000
5000000
6000000
7000000
8000000
9000000
10000000
11000000
12000000
13000000
14000000
15000000
16000000
17000000
18000000
19000000
20000000
21000000
22000000
65.1
0
128.
6012
9.27
129.
6513
0.14
132.
2013
3.98
144.
2314
4.30
146.
50
165.
58
144145
f1 (ppm)
144.23
144.30
128.5129.0129.5130.0130.5
f1 (ppm)
128.60
129.27
129.65
130.14
Figure S36. 13C NMR (101 MHz, D2O) spectrum of (BNA)Br.
-3-2-1012345678910111213141516
f1 (ppm)
May29-2019-DL-0529-2/3
2.04
2.07
1.05
2.02
1.00
0.96
1.80
3.07
0.02
3.19
4.31
4.76
4.78
5.26
7.18
7.27
7.28
7.35
7.37
Figure S37. 1H NMR (400 MHz, CDCl3) spectrum of BNAH.
23 / 44
Page 24
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
-100
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
May29-2019-DL-0529/5
22.8
8
57.4
2
77.0
2
98.6
410
3.20
127.
1812
7.80
128.
8312
8.99
137.
2414
0.05
170.
10
126.5127.0127.5128.0128.5129.0129.5
f1 (ppm)
0
500
1000127.
18
127.
80
128.
8312
8.99
Figure S38. 13C NMR (101 MHz, CDCl3) spectrum of BNAH.
-3-2-1012345678910111213141516
f1 (ppm)
Jun-25-2019-DL-0625-2
Jun-25-2019-DL-0625-2
2.51
3.34
5.79
7.45
7.46
7.52
7.54
8.07
8.08
8.09
8.10
8.46
8.48
9.02
9.04
9.13
Figure S39. 1H NMR (400 MHz, DMSO-d6) spectrum of (DMPY)PF6.
24 / 44
Page 25
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
Jun-25-2019-DL-0625-2
Jun-25-2019-DL-0625-2
18.4
0
40.0
0
63.7
8
128.
2612
9.15
129.
6912
9.83
134.
7613
9.79
142.
5414
4.72
146.
79
Figure S40. 13C NMR (101 MHz, DMSO-d6) spectrum of (DMPY)PF6.
25 / 44
Page 26
1.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
f1 (ppm)
0
50
100
150
200
250
300
350
400
450
Jun-27-2019-DL-0627-5/14
2.06
3.03
4.33
7.09
* * * *
26 / 44
Page 27
Figure S41. (top) 1H NMR spectrum of (BNA)PF6 in D2O : methanol-d4 (1:1) (Blue line) and 1H NMR spectrum of the mixture of
(BNA)PF6 and Ru(tpy)(biq)(HCOO)PF6 in D2O : methanol-d4 (1:1) under dark condition for 3 h (Red line, * denotes the in-situ
generated 1,4-BNAH including coordinated 1,4-BNAH 4); (middle) 1H NMR spectrum of the mixture of 10mM (BNA)PF6 and 10 mM 7b
in acetonitrile-d6 within 5 min (# denotes the generated 1,4-BNAH); (bottom) 1H NMR spectrum of the reaction mixture of (BNA)PF6
and DCOONa in the presence of 7 after 1h irradiation (Reaction conditions: 0.5M DCOONa, 1mM (BNA)PF6, 20 uM 7, 10 mL water
and 80 w green LEDs, after 1h irradiation the mixture extracted with 2 mLX3 chloroform).
27 / 44
Page 28
Figure S42. 1H NMR spectrum of the mixture of 1b and Ru(tpy)(biq)(MeCN)PF6 in acetonitrile-d6 after 0.5 h at room temperature.
-17-16-15-14-13-12-11-10-9-8-7-6-5-4-3-2-101234567891011123
f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
6500
7000
Jun-12-2019-DL-0612-2/16
-15.05-14.95-14.85-14.75-14.65-14.55-14.45
f1 (ppm)
-14.
71-1
4.69
1b7b
Figure S43. 1H NMR spectrum of the mixture of 1b and Ru(tpy)(biq)(MeCN)PF6 in acetonitrile-d6 after 21 h at room temperature.
28 / 44
Page 29
-17-16-15-14-13-12-11-10-9-8-7-6-5-4-3-2-101234567891011123
f1 (ppm)
-200
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
3200
3400
3600
Jun-12-2019-DL-0612-1/15
-14.
71
-16.0-15.5-15.0-14.5-14.0-13.5
f1 (ppm)
-14.
71
7b
Figure S44. 1H NMR spectrum of the mixture of 7b and Ru(tpy)(bpy)(MeCN)PF6 in acetonitrile-d6 after 21 h at room temperature.
-1-16-15-14-13-12-11-10-9-8-7-6-5-4-3-2-101234567891011123
f1 (ppm)
Jul-08-2019-DL-0708-1
DL-0708-1-1h
Figure S45 1H NMR spectrum of the mixture of 7b and (DMPY)PF6 in acetonitrile-d6 after 1 h at room temperature.
29 / 44
Page 30
-1-16-15-14-13-12-11-10-9-8-7-6-5-4-3-2-101234567891011123
f1 (ppm)
Jul-09-2019-DL-0709-1
DL-0709-1-24h
0.23
5.33
1.16
9.28
0.97
5.26
3.51
0.58
9.32
1.73
0.23
1.85
1.54
0.29
9.73
1.82
0.35
8.59.09.510.010.511.0
f1 (ppm)
3.54.04.55.05.56.0
f1 (ppm)
1.41.61.82.02.22.42.62.8
f1 (ppm)
+
*
# #
#
#
##
=
=
=
=
=
=
$
$
K = [1.82*(1.54+0.29)] / [0.35*(9.32/3)] = 3.06
+
*
# #
#
#
#
=
=
=
=
=
$
$
Figure S46. 1H NMR spectrum of the mixture of 7b and (DMPY)PF6 in acetonitrile-d6 after 24 h at room temperature. (Chemical shifts
denoted +, *, #, = and $ are corresponding to 7b, [Ru(tpy)(biq)S]2+, 1,6-DHDMPY, 1,4-DHDMPY and DMPY)
-17-16-15-14-13-12-11-10-9-8-7-6-5-4-3-2-101234567891011123
f1 (ppm)
-100
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700
1800
0.93
26.8
54.
7348
.28
3.52
27.9
118
.42
2.10
47.9
99.
770.
769.
268.
151.
0050
.81
7.58
1.00
K= [7.58*(8.15+1)] / [1*(48.28/3)] = 4.3
8.59.09.510.0
f1 (ppm)
Jul-10-2019-DL-0710-1/1
4.04.55.05.56.0
f1 (ppm)
1.52.02.53.03.5
f1 (ppm)
+
*
##
#
#
##
=
=
=
=
=
=
$
$
Figure S47. 1H NMR spectrum of the mixture of 7b and (DMPY)PF6 in acetonitrile-d6 after 48 h at room temperature. (Chemical shifts
denoted +, *, #, = and $ are corresponding to 7b, [Ru(tpy)(biq)S]2+, 1,6-DHDMPY, 1,4-DHDMPY and DMPY)
30 / 44
Page 31
-17-16-15-14-13-12-11-10-9-8-7-6-5-4-3-2-101234567891011123
f1 (ppm)
-200
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
0.93
24.7
05.
0466
.66
4.18
26.5
716
.77
1.49
67.2
99.
810.
479.
608.
651.
7768
.96
9.18
1.00
8.59.09.510.0
f1 (ppm)
Jul-11-2019-DL-0711-1/2
DL-0711-1-72h
4.04.55.05.56.06.5
f1 (ppm)
1.52.02.53.03.5
f1 (ppm)
+
*
#
# #
#
#
#
= =
=
=
=
=
$
$
+
K= [9.18*(8.65+1.77)] / [1*(66.66/3)] = 4.31
Figure S48. 1H NMR spectrum of the mixture of 7b and (DMPY)PF6 in acetonitrile-d6 after 72 h at room temperature. (Chemical shifts
denoted +, *, #, = and $ are corresponding to 7b, [Ru(tpy)(biq)S]2+, 1,6-DHDMPY, 1,4-DHDMPY and DMPY)
-17-16-15-14-13-12-11-10-9-8-7-6-5-4-3-2-101234567891011123
f1 (ppm)
-200
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
3200
3400
3600
Jul-12-2019-DL-0712-1/3
0.97
40.0
211
8.38
4.88
41.0
626
.23
0.76
1.94
115.
9716
.32
0.38
14.3
513
.20
2.07
107.
1111
.99
1.00
K = [11.99*(13.20+2.07)] / [1*(118.38/3)] = 4.6
Figure S49. 1H NMR spectrum of the mixture of 7b and (DMPY)PF6 in acetonitrile-d6 after 96 h at room temperature.
31 / 44
Page 32
-1-16-15-14-13-12-11-10-9-8-7-6-5-4-3-2-101234567891011123
f1 (ppm)
Jul-15-2019-DL-0715-1
DL-0715-1-7day
0.88
93.9
531
.93
19.2
0
95.3
7
11.7
210
.65
1.63
10.7
8
1.00
K = [10.78*(10.65+1.63)] / [1*(93.95/3)] = 4.23
Figure S50. 1H NMR spectrum of the mixture of 7b and (DMPY)PF6 in acetonitrile-d6 after 7 days at room temperature.
32 / 44
Page 33
Electronic absorption spectra
350 400 450 500 550 600 650 700 750
0.0
0.1
0.2
0.3
0.4
0.5
A
Wavelength (nm)
a)
0 50 100 150 200 250 3000.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
A (a
t 625
nm
)
Time (s)
Model ExpDecay1
Equation y = y0 + A1*exp(-(x-x0)/t1)t1 50.64563 ± 3.18448k 0.020±0.001R-Square (COD) 0.99414
b)
Figure S51. a) Electronic absorption spectra of 7 in 0.1 M HCOONa aqueous solution under green light (40 w) for 5 min at 298 K; b)
Time course of the change in absorption of 7 at 625 nm.
33 / 44
Page 34
350 400 450 500 550 600 650 700 750
0.0
0.1
0.2
0.3
0.4
0.5A
Wavelength (nm)
a)
0 50 100 150 200 250 300
0.05
0.10
0.15
0.20
A (a
t 625
nm
)
Time (s)
Model ExpDecay1Equation y = y0 + A1*exp(-(x-x0)/t1)t1 34.89146 ± 2.05766k 0.028 ± 0.002R-Square (COD) 0.99499
b)
Figure S52. a) Electronic absorption spectra of 7 in 0.2 M HCOONa aqueous solution under green light (40 w) for 5 min at 298 K; b)
Time course of the change in absorption of 7 at 625 nm.
34 / 44
Page 35
350 400 450 500 550 600 650 700 750
0.0
0.1
0.2
0.3
0.4
0.5A
Wavelength (nm)
a)
0 50 100 150 200 250 300
0.08
0.10
0.12
0.14
0.16
0.18
0.20
0.22
A (a
t 625
nm
)
Time (s)
b)
ExpDecay1 Model:y = y0 + A1*exp[-(x-x0)/t1]t1 = 29.34 ±1.29 sk = 0.034 ± 0.002 s-1
R2 = 0.9971
Figure S53. a) Electronic absorption spectra of 7 in 0.5 M HCOONa aqueous solution under green light (40 w) for 5 min at 298 K; b)
Time course of the change in absorption of 7 at 625 nm.
35 / 44
Page 36
350 400 450 500 550 600 650 700 750
0.0
0.1
0.2
0.3
0.4
0.5A
Wavelength (nm)
a)
0 50 100 150 200 250 3000.04
0.08
0.12
0.16
0.20
0.24
0.28
A (a
t 625
nm
)
Time (s)
Model ExpDecay1
Equation y = y0 + A1*exp(-(x-x0)/t1t1 20.4037 ± 1.10521E-8k 0.049±0.002R-Square (COD) 0.99584
b)
Figure S54. a) Electronic absorption spectra of 7 in 1 M HCOONa aqueous solution under green light (40 w) for 5 min at 298 K; b) Time
course of the change in absorption of 7 at 625 nm.
250 300 350 400 450 500 550 600 650 700 750 8000.0
0.2
0.4
0.6
0.8
A
Wavelength (nm)
1MLCT at 473 nm
50 uM Ru(tpy)(bpy)Cl2 in water(ε473 nm = 5368 mol-1cm-1 )(ε456 nm = 5142 mol-1cm-1)
Figure S55. Electronic absorption spectrum of 1 in H2O.
36 / 44
Page 37
250 300 350 400 450 500 550 600 650 700 750 8000.0
0.2
0.4
0.6
0.8
1.0
A
Wavelength (nm)
1MLCT at 548 nm
50 uM RuTPYBIQCl2 in water(ε548 nm = 4723 mol-1cm-1 )(ε525 nm = 3761 mol-1cm-1)
Figure S56. Electronic absorption spectrum of 7 in H2O.
250 300 350 400 450 500 550 600 650 700 750 8000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
A
Wavelength (nm)
1MLCT at 555 nm
50 uM RuTPYBIQ(HCOO)PF6 in water(ε555 nm = 5739 mol-1cm-1 )
250 300 350 400 450 500 550 600 650 700 750 8000.0
0.2
0.4
0.6
0.8
1.0A
Wavelength (nm)
1MLCT at 606 nm
50 uM Ru(tpy)(biq)(H)PF6 in MeCN(ε606 nm = 7514 mol-1cm-1 )
Figure S57. (left) Electronic absorption spectrum of Ru(tpy)(biq)(Cl)PF6 in H2O; (right) Electronic absorption spectrum of
Ru(tpy)(biq)(H)PF6 in MeCN; (bottom)
37 / 44
Page 38
Molecular structures
Figure S58. Molecular structure of [Ru(tpy)(biq)Cl]+ . Ellipsoids were drawn at 50 % probability and hydrogen atoms were omitted for
clarity. (CCDC number: 1920316)
Figure S59. Molecular structure of [Ru(tpy)(biq)MeCN]2+. Ellipsoids were drawn at 50 % probability and hydrogen atoms were omitted
for clarity. (CCDC number: 1920254)
Figure S60. Molecular structure of [Ru(tpy)(biq)HCOO]+. Ellipsoids were drawn at 50 % probability and hydrogen atoms were omitted
for clarity. (CCDC number: 1942074)
38 / 44
Page 39
Table S1. Crystal data and refinement results for compounds Ru(tpy)(biq)(Cl)PF6, Ru(tpy)(biq)(MeCN)(PF6)2 and Ru(tpy)(biq)(HCOO)PF6
Compounds Ru(tpy)(biq)(Cl)PF6 Ru(tpy)(biq)(MeCN)(PF6)2 Ru(tpy)(biq)(HCOO)PF6
Crystal description Purple block Purple block Purple rod
Crystal size (mm) 0.40 x 0.35 x 0.20 0.17 x 0.09 x 0.05 0.30 x 0.26 x 0.04
Crystal system triclinic triclinic triclinic
Space group P1 P1 P1
a (Å) 13.5920(11) 12.8940(11) 11.1590(11)
b (Å) 13.6081(11) 12.8940(11) 12.3059(12)
c (Å) 14.0589(12) 12.9630(12) 14.8631(13)
α (°) 64.306(2) 82.985(2) 67.8750(10)
β (°) 73.922(4) 66.9870(10) 68.0450(10)
γ (°) 64.168(3) 88.659(2) 86.116(3)
V (Å3) 2096.63 1968.1 1747.3(3)
Z 2 0 2
μ (mm-1) 0.668 0.710 0.569
Total/unique reflections 10171 / 7153 10005 / 6807 8928 / 6060
Rint 0.0436 0.0906 0.0941
R[F2 > 2σ(F2)] 0.0635 0.0980 0.0942
wR2 (F2) 0.1569 0.2296 0.2165
GOF 1.046 1.095 1.136
No. of parameters 551 533 483
Δρmax /Δρmin (e Å-3) 0.983 / -1.084 2.096 / -2.021 1.591 / -1.072
CCDC 1920316 1920254 1942074
39 / 44
Page 40
Mass spectra
Figure S61. Mass spectum of 1 in MeOH.
Figure S62. Mass spectum of 2 in MeOH.
Figure S63. Mass spectum of 3 in MeOH.
245.1366
304.2619526.0389
585.5343
+MS, 0.2-0.4min #(12-23)
0.0
0.5
1.0
1.5
2.06x10
Intens.
100 200 300 400 500 600 700 800 m/z
413.2676
550.0373
+MS, 0.4min #(24), Background Subtracted
0
20
40
60
80
100
Intens.[%]
400 450 500 550 600 650 700 750 m/z
554.0684
+MS, 0.3-0.3min #(16-18), Background Subtracted
0
20
40
60
80
100
Intens.[%]
300 400 500 600 700 800 m/z
40 / 44
Page 41
Figure S64. Mass spectum of 4 in MeOH.
Figure S65. Mass spectum of 5 in MeOH
Figure S66. Mass spectum of 6 in MeOH.
586.0583
648.5570
+MS, 0.5-0.5min #(27-28), Background Subtracted
0
20
40
60
80
100
Intens.[%]
400 450 500 550 600 650 700 750 800 m/z
172.0947
301.1392414.9749
576.0274
+MS, 0.5-0.5min #(28-30), Background Subtracted
0
20
40
60
80
Intens.[%]
0 200 400 600 800 1000 1200 1400 m/z
356.9825 413.2670
554.0683
609.0399
+MS, 0.4-0.5min #(26-27), Background Subtracted
0
20
40
60
80
Intens.[%]
400 500 600 700 800 m/z
41 / 44
Page 42
Figure S67. Mass spectum of 7 in MeOH.
Figure S68. Mass spectum of 7 in H2O.
Figure S69. Mass spectum of Ru(tpy)(biq)(MeCN)(PF6)2 in MeOH.
436.1845464.2158
626.0611
649.0642
697.6490
+MS, 0.5-0.5min #(30-31)
0
20
40
60
Intens.[%]
400 450 500 550 600 650 700 750 800 m/z
295.5508
608.1059
+MS, 0.3-0.4min #(17-22), Background Subtracted
0
20
40
60
80
100
Intens.[%]
200 400 600 800 1000 m/z
610.0910
777.0716
+MS, 0.5-0.5min #(27-28), Background Subtracted
0
2
4
6
8
10
12
Intens.[%]
400 500 600 700 800 900 m/z
42 / 44
Page 43
Figure S70. Mass spectum of 7 and HCOONa in H2O after irradiation.
Figure S71. Mass spectum of Ru(tpy)(biq)(HCOO)PF6 in MeOH.
Figure S72. Mass spectum of Ru(tpy)(biq)(H)PF6 in MeOH.
608.1054
636.0993
+MS, 0.6min #(34), Background Subtracted
0
20
40
60
Intens.[%]
500 550 600 650 700 750 m/z
636.0981
+MS, 0.5min #(30), Background Subtracted
0
20
40
60
80
100
Intens.[%]
400 500 600 700 800 900 m/z
475.3257
531.8703
592.1086
626.0682701.4944
+MS, 0.4min #(26), Background Subtracted
0
20
40
60
80
Intens.[%]
500 550 600 650 700 750 m/z
43 / 44
Page 44
Figure S73. Mass spectum of Ru(tpy)(bpy)(H)PF6 in MeOH. [Note: Ru(tpy)(bpy)(H)PF6 is sensitive to CO2 and [Ru(tpy)(bpy)(HCOO)]+
was detected.]
References
1 Kuhn, H., Braslavsky, S. & Schmidt, R. Chemical actinometry (IUPAC technical report). Pure and
Applied Chemistry 2004, 76, 2105-2146.
2 Sun, X., Chen, J. T. & Ritter, T. Catalytic dehydrogenative decarboxyolefination of carboxylic acids.
Nat. Chem. 2018, 10, 1229-1233.
3 Wegner, E. E. & Adamson, A. W. Photochemistry of Complex Ions .3. Absolute Quantum Yields for
Photolysis of Some Aqueous Chromium(3) Complexes . Chemical Actinometry in Long Wavelength
Visible Region. J. Am. Chem. Soc. 1966, 88, 394.
4 Kobayashi, A., Takatori, R., Kikuchi, I., Konno, H., Sakamoto, K. & Ishitani, O. Formation of novel 1 :
1 adducts accompanied by regioselective hydride transfer from transition-metal hydrido complexes to
NAD(P) models. Organometallics 2001, 20, 3361-3363.
356.9801
413.2662
475.3242
536.0672
636.0996701.4952
814.5809
+MS, 0.4-0.5min #(26-27), Background Subtracted
0
20
40
60
80
100
Intens.[%]
400 500 600 700 800 m/z
44 / 44
