Photoinduced_Electron_Transfer_中科院光功能材料.ppt

Distance effect ? Long range photoinduced electron transfer (electron transfer via superexchange) D* - S - A D + - S - A – D - S + - A - D + - S - - A ( virtual states ) Distance effect Distance effect Distance effect Distance effect Distance effect Distance effect Distance effect Distance effect Distance effect Charge transfer complex Charge transfer complex Charge transfer complex Driving force 1 electrostatic interaction due to undistorted electron clouds (dipole-dipole forces) 2 polarization interaction (the results of an electron distribution of D distorted by A) 3 exchange repulsion (due to exchange of electron between D and A) 4 charge transfer (electron delocalization of electrons from HOMO of D to LUMO of A) 5 coupling (other higher order interactions) Accts. Chem. Res ., 10 (1977), 294 Charge transfer complex Foster , R. “ Organic Charge-Transfer Compolexes ” Academic Press, new York, 1969 A bona fide complex is a molecular association of two or more components which in principle constitutes an independent crystal structure in the solid state, but which is dissociated in the gas phase or in solution. Charge transfer complex A + D [A,D] Complex binding energy: (0.6 kcal/mol at 25 ? C) kT - ? H 10 kcal/mol Charge transfer complex donors (aromatic hydrocarbons, aniline derivatives) acceptors (quinones, TCNE) K 0.5 ~ 5 M -1 ? H -3 ~ -5 kcal/mol ? S -8 ~ -15 eu D Et-O-CH=CH 2 A TCNE ? V = -4 mL/mol D enol ether A TCNE ? V = -30 mL/mol Charge transfer complex ? Absorption spectroscopy of CT complex ? CT = a ? (A,D) + b ? (A-.,D+.) ? CT* = a* ? (A,D) + b* ? (A-.,D+.) ground state CT a b less polar low dipole moments (2 ~ 4 D) (Py-TCNE: 2.0 D) small solvatochromic effect excited state CT b* a* ionic Broad absorption band Charge transfer complex ? Absorption spectroscopy of CT complex h ? CT = n F [ E(1/2) ox – E(1/2) red ] + C (for neutral D and A in common organic solvents, C = 1.0