TY - JOUR
T1 - Variation of excitation energy influences the product distribution of a two-step electron transfer
T2 - S2 vs S1 electron transfer in a Zn(II)porphyrin-viologen complex
AU - Petersson, Jonas
AU - Eklund, Mattias
AU - Davidsson, Jan
AU - Hammarström, Leif
PY - 2009/6/17
Y1 - 2009/6/17
N2 - (Figure Presented) We have, for the first time for molecular systems in solution, shown a case where the variation of excitation energy influences the product distribution of a two-step electron transfer. The photoexcitation was to the porphyrin-localized S2 state or either of the S1(v = 1) or S1(v = 0) states of an aqueous Zn(II)-meso- tetrasulphonatophenyl-porphyrin-methylviologen (ZnTPPS4-/MV 2+) complex. Both forward and back electron transfer occur on a subpicosecond time scale (τFET ≈ 0.2, τBET = 0.7 ps). The excess energy of the higher excitations partially survives both electron transfer steps. This is seen by different distributions of unrelaxed ground states, which are generated by the back electron transfer and has unique UV-vis spectroscopic signatures. State selective electron transfer opens interesting possibilities for reaction control, and the results represent initial steps in that direction
AB - (Figure Presented) We have, for the first time for molecular systems in solution, shown a case where the variation of excitation energy influences the product distribution of a two-step electron transfer. The photoexcitation was to the porphyrin-localized S2 state or either of the S1(v = 1) or S1(v = 0) states of an aqueous Zn(II)-meso- tetrasulphonatophenyl-porphyrin-methylviologen (ZnTPPS4-/MV 2+) complex. Both forward and back electron transfer occur on a subpicosecond time scale (τFET ≈ 0.2, τBET = 0.7 ps). The excess energy of the higher excitations partially survives both electron transfer steps. This is seen by different distributions of unrelaxed ground states, which are generated by the back electron transfer and has unique UV-vis spectroscopic signatures. State selective electron transfer opens interesting possibilities for reaction control, and the results represent initial steps in that direction
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U2 - 10.1021/ja900729j
DO - 10.1021/ja900729j
M3 - Article
C2 - 19463018
AN - SCOPUS:67650534972
VL - 131
SP - 7940
EP - 7941
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 23
ER -