Intramolecular electron transfer in cyanide-bridged ruthenium dimers

被引：11

作者：

Ponce, A ^{[1
]}

Bachrach, M ^{[1
]}

Farmer, PJ ^{[1
]}

Winkler, JR ^{[1
]}

机构：

[1] CALTECH,BECKMAN INST,PASADENA,CA 91125

来源：

INORGANICA CHIMICA ACTA | 1996年 / 243卷 / 1-2期

基金：

美国国家科学基金会;

关键词：

electron-transfer; mixed-valence complexes; ruthenium complexes; cyanide complexes;

D O I：

10.1016/0020-1693(95)04900-2

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The absorption, luminescence, and transient-absorption spectra of [(bpy)(tpy)Ru-II(CN)](+) (bpy = 2,2'-bipyridine; tpy = 2,2':6'2 ''-terpyridine) and [(bpy)(tpy)(RuCNRuII,III)-C-II(NH3)(5)](3+,4+) have been measured. Metal-to-ligand charge-transfer (MLCT) excitation of the monomer produces an excited state that decays with a rate constant of 1.3 x 10(8) s(-1). Picosecond excitation of [(bpy)(tpy)Ru(II)CNRU(III)(NH3)(5)](4+) does not lead to any detectable transients, indicating that relaxation rate constants are >10(12) s(-1). A transient attributable to [(bpy)(tpy(.-))Ru(II)CNR(III)(NH3)(5)](3+) is observed following picosecond excitation of [(bpy)(tpy)RuCNRuII(NH3)(5)](3+); this intermediate decays via intramolecular electron transfer with a rate constant of 3.8 x 10(10) s(-1). Quantum-mechanical descriptions of the nuclear reorganization accompanying electron transfer are required to explain the observed kinetics.

引用

页码：135 / 140

页数：6

共 29 条

[11] ULTRAFAST ELECTRON-TRANSFER AND COUPLED VIBRATIONAL DYNAMICS IN CYANIDE BRIDGED MIXED-VALENCE TRANSITION-METAL DIMERS [J].