PORPHYRIN-QUINONE ELECTRON-TRANSFER REVISITED - THE ROLE OF EXCITED-STATE DEGENERACY IN ULTRAFAST CHARGE-TRANSFER REACTIONS

被引:61
作者
WYNNE, K [1 ]
LECOURS, SM [1 ]
GALLI, C [1 ]
THERIEN, MJ [1 ]
HOCHSTRASSER, RM [1 ]
机构
[1] UNIV PENN,DEPT CHEM,PHILADELPHIA,PA 19104
关键词
D O I
10.1021/ja00118a011
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Ultrafast time-resolved anisotropy experiments in which electronically excited [5-(1',4'-benzoquinonyl)-10,1 5,20-triphenylporphinato]magnesium (MgPQ) was probed with polarization both parallel and perpendicular to the pump pulse have been carried out in a variety of solvents. These results show that the photoinduced electron transfer process involving the locally-excited MgP*Q state is solvent independent, while the thermal charge recombination reaction is solvent dependent. Moreover, these studies indicate that the photoinduced charge separation reaction may be rate-limited by electronic population equilibration between near degenerate porphyrin Q(x) and Q(y) levels.
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页码:3749 / 3753
页数:5
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