期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 131, 期 2, 页码 577-584出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja806261q
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资金
- Ministry of Education, Culture, Sports, Science and Technology, Japan [18033033, 19205019, 19750034]
- Japan Science and Technology Agency (JST)
- Grants-in-Aid for Scientific Research [18033033, 19750034] Funding Source: KAKEN
Kinetics of photoinduced electron transfer from a series of electron donors to the triplet excited states of a series of nonplanar porphyrins, hydrochloride salts of saddle-distorted dodecaphenylporphyrin ([H4DPP]Cl-2), tetrakis(2,4,6-trimethylphyenyl)porphyrin ([H4TMP]Cl-2), tetraphanylporphyrin ([H4TPP]Cl-2), and octaphenylporphyrin ([H4OPP]Cl-2), were investigated in comparison with those of a planar porphyrin, zinc [tetrakis(pentafluorophenyl)]porphyrin [Zn(F20TPP)(CH3CN)], in deaerated acetonitrile by laser flash photolysis. The resulting data were evaluated in light of the Marcus theory of electron transfer, allowing us to determine reorganization energies of electron transfer to be 1.21 eV for [H4TMP]Cl-2, 1.29 eV for [H4TPP]Cl-2, 1.45 eV for [H4OPP]Cl-2, 1.69 eV for [H4DPP]Cl-2, and 0.84 eV for [Zn(F20TPP)(CH3CN)]. The reorganization energies exhibited a linear correlation relative to the out-of-plane displacements, which represent the degree of nonplanarity. The rate of electron-transfer reduction of diporotonated porphyrins is significantly slowed down by conformational distortions of the porphyrin ring. This indicates that the reorganization energy of electron transfer is governed by structural change, giving a larger contribution of inner-sphere bond reorganization energy rather than outer-sphere solvent reorganization energy.
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