Photoinduced electron transfer reactions of N,N,N’, N’- tetramethylbenzidine (TMB) with several electron poor olefins in acetonitrile solution have been studied by using laser flash photolysis and steady-state fluor...Photoinduced electron transfer reactions of N,N,N’, N’- tetramethylbenzidine (TMB) with several electron poor olefins in acetonitrile solution have been studied by using laser flash photolysis and steady-state fluorescence quenching method. The triplet state of TMB at 480nm was found to undergo reductive quenching with the elec- tron acceptors of fumaronitrile, dimethyl fumarate, cinnamonitrile, crotononitrile and diethyl fumarate. The detec- tion of ion radical intermediates in the photolysis reactions confirms the proposed electron transfer mechanism, as expected from thermodynamics. The quenching rate constants of triplet TMB were determined at 510nm, where all the kq values approach or reach to diffusion controlled limit. In addition, fluorescence quenching rate constant T kq was also obtained by calculating with Stern-Volmer equation.展开更多
基金supported by the National Key R&D Program of China (Grant Nos. 2018YFA0209101 and 2017YFA0303700)the National Science Foundation of China (Grant NOs. 21922302, 21873047, 91833305, and 91850105)
文摘Photoinduced electron transfer reactions of N,N,N’, N’- tetramethylbenzidine (TMB) with several electron poor olefins in acetonitrile solution have been studied by using laser flash photolysis and steady-state fluorescence quenching method. The triplet state of TMB at 480nm was found to undergo reductive quenching with the elec- tron acceptors of fumaronitrile, dimethyl fumarate, cinnamonitrile, crotononitrile and diethyl fumarate. The detec- tion of ion radical intermediates in the photolysis reactions confirms the proposed electron transfer mechanism, as expected from thermodynamics. The quenching rate constants of triplet TMB were determined at 510nm, where all the kq values approach or reach to diffusion controlled limit. In addition, fluorescence quenching rate constant T kq was also obtained by calculating with Stern-Volmer equation.
