Effects of driving force on the rates of intramolecular and bimolecular electron-transfer reactions

摘要

Intramolecular　electron transfer(ET)in ［Ir_2(μ-pz*)_2(CO)_2(Ph_2PO(CH_2)_2A+)_2］［B(Ph)_~-_4］_2 (［IrPOpy~+］_2; pz*=3,5-dimethylpyrazolyl, A=pyridinium derivative, Ph=C_6H_5)exhibits a Gaussian free-energy dependence. The temperature dependences(200-280 K)of both Excited-state ET(Ir_2*→A~+)and highly exergonic recombination(A·→Ir_2·)reactions also Agree remarkably well with semiclassical ET theory.