Supporting Information
Electron transfer reactions of sulfur containing amino acids with
Photochemically generated ruthenium(III)- polypyridyl complexes
Characterization
All the final products were characterized by UV-Vis, IR, 1H-NMR,
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C-NMR and ESI-
MS to prove that compounds were pure enough for the spectroscopic measurements.
(a) Tris(2,2-bipyridine)ruthenium(II) chloride
The purity of the sample was checked by recording absorption (
= 14,600 M-1 cm-1) and emission (
λ em
max
λ ab
max
= 452 nm and 452
= 600 nm) spectra.4 FTIR (KBr) cm-1: 1621, 1484, 896,
464. 1H-NMR (DMSO): δ=8.94 (dd, 6H), 8.18 (dd, 6H), 7.82 (m, 6H), 7.60 (m 6H).
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C-NMR
(125 MHz, DMSO) δ= 157.02, 151.64, 138.41, 128.37, 125.05. ESI-MS: 285 m/z, [M]2+ calcd
for [C30H24N6Ru], 605 m/z [M]+ calcd for [C30H24ClN6Ru]+
(b) Tris(4,4-dimethyl-2,2-bipyridine)ruthenium(II) chloride
The purity of the sample was checked by recording absorption ( λ ab
max = 460 nm and 460
-1
= 14,300 M-1cm-1) and emission ( λ em
max = 610 nm) spectra. FTIR (KBr) cm : 2975 (C-H), 1608,
1469 (C=N & C=C), 827 (C-H aromatic), 470 (Ru-N). 1H-NMR (DMSO): δ = 8.74 (s, 6H), 7.54
(d, 6H), 7.35 (dd, 6H), 2.65 (s 18H (me)).
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C-NMR (125 MHz, DMSO) δ= 156.66, 150.67,
149.78, 128.91, 125.50, 21.16. ESI-MS: 653 m/z, [M]+, 327 m/z [M]2+ calcd for [C36H36N6Ru]+
(c) Tris(4,4-di-tert-butyl-2,2-bipyridine)ruthenium(II) chloride
The purity of the sample was checked by recording absorption ( λ ab
max = 456 nm and 456
= 16,800 M-1 cm-1) and emission (
λ ab
max
= 456 nm and 456 = 16,800 M-1 cm-1) and emission
1
(
λ em
max
= 600 nm) spectra.3 FTIR (KBr) cm-1: 3048, 2954, 1608, 1469, 846, 460. 1H-NMR
(DMSO): δ= 8.86 (d, 6H), 7.57 (d, 6H), 7.52 (d, 6H), 1.4 (s 54H (-C(CH3)3).
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C-NMR (125
MHz, DMSO) δ= 162.15, 156.86, 150.86, 125.21, 122.35, 35.96, 30.53. ESI-MS: 453 m/z, calcd
for [C54H72N6Ru]+
(d) Tris(1,10-phenanthroline)ruthenium(II) chloride
The purity of the sample was checked by recording absorption (
= 18,100 M-1 cm-1) and emission (
λ ab
max
λ ab
max
= 447 nm and 447
= 600 nm) spectra.5 FTIR (KBr) cm-1: 1627, 1089,
3052 and 472. 1H-NMR (DMSO): δ= 8.76 (d, 6H), 8.41 (s, 6H), 8.09 (d, 6H), 7.80(t, 6H)
C-NMR (125 MHz, DMSO) δ= 153.21, 147.70, 137.30, 130.91, 128.51, 126.77. ESI-MS: 677
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m/z, [M-Cl]+ calcd for [C36H24ClN6Ru]+.
(e) Tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) chloride
The purity of the sample was checked by recording absorption (
= 29,500- M-1 cm-1) and emission (
λ ab
max
λ ab
max
= 460 nm and 460
=610 nm) spectra.5 FTIR (KBr) cm-1: 3407, 3053,
1625, 1415, 1209 and 472. 1H-NMR (DMSO): δ= 8.36 (d, 6H), 8.29 (s, 6H), 7.85 (d, 6H), 7.67
(m 30H).
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C NMR (125 MHz, DMSO) δ= 152.88, 148.53, 135.89, 130.39, 130.16, 129.65,
128.63, 127.02, 126.56. ESI-MS: 1134 m/z, [M-Cl]+ calcd for [C72H48ClN6Ru]+ .
(f) Tetrasodium tris[1,10-phenanthrolinediyl-4,7-di(benzene sulphanato)ruthenate(II)
hexahydrate. Na4 [Ru(dpsphen)3]4 –
The purity of the sample was checked by recording absorption (
= 28,500 M-1 cm-1) and emission (
λ ab
max
λ ab
max
= 460 nm and 460
=610 nm) respectively, which are in close agreement
with the reported values.4 FTIR (KBr) cm-1: 3502, 3068, 2366, 1643, 1625. 1H-NMR (DMSO):
δ= 8.40 (d, 6H), 8.20 (s, 6H) 7.91(s, 6H), 7.81 (d, 12H), 7.63 (m, 12H).
DMSO)
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C NMR (125 MHz,
δ= 152.97, 149.59, 148.47, 148.28, 135.50, 133.46, 130.35, 129.14, 128.70, 127.38,
127.08, 126.3.
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Figure Caption
Fig. S1 1H NMR spectrum of product after oxidation of methionine with [Ru(dmbpy)3]3+
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Fig. S2 FT-IR spectrum of product after oxidation of methionine with [Ru(dmbpy)3]3+
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Fig. S3 Plot of log OD vs time for the reaction of [Ru(dmbpy)3]3+ with methionine.
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Fig. S4 Transient absorption spectrum of [Ru(bpy)3]2+ in the absence of methionine in
deoxygenated aqueous CH3CN (1:1, v/v) solution obtained at different time delays: from 100 ns
to 2 μs.
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Fig. S5 Transient absorption spectra recorded on [Ru(dmbpy)3]2+ in the oxygen-saturated
aqueous CH3CN (1:1, v/v) solution in the absence of methionine obtained at different time
delays: 100 ns to 2 μs.
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