EVALUATION OF CHARGE RESONANCE CHARACTER IN THE EXCITED TRIPLET DIMERS STUDIED BY TIME-RESOLVED ELECTRON-PARAMAGNETIC-RESONANCE - AROMATIC RING-BRIDGED PORPHYRIN DIMERS

被引:34
作者
ISHII, K
YAMAUCHI, S
OHBA, Y
IWAIZUMI, M
UCHIYAMA, I
HIROTA, N
MARUYAMA, K
OSUKA, A
机构
[1] TOHOKU UNIV,INST CHEM REACT SCI,SENDAI,MIYAGI 980,JAPAN
[2] KYOTO UNIV,FAC SCI,DEPT CHEM,KYOTO 606,JAPAN
关键词
D O I
10.1021/j100089a013
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Zero-field splittings (zfs) of the lowest excited triplet states were obtained by time-resolved EPR for aromatic ring-bridged porphyrin dimers having different interplanar distances. The zfs parameter D (= -3Z/2) of the dimer decreased with decreasing the interplanar distance (R). From comparison of the D value of the dimer with that of the corresponding monomer, a contribution of CR character (b(2)) was evaluated as a function of R. An interplanar resonance integral (beta(1) + beta(2)) was estimated from b(2) and the magnitude of a red shift of T-1 (Delta E(T-1)). b(2) and beta(1) + beta(2) correlated well with both of Delta E(T-1) and the triplet lifetime in the dimer. All the results were interpreted well in terms of delocalization of excitation over the dimer molecule, namely the charge resonance interaction.
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页码:9431 / 9436
页数:6
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