Superexchange-Mediated Charge Separation and Charge Recombination in Covalently Linked Donor - Bridge - Acceptor Systems

Abstract

Evidence is presented in support of the concept that electron transfer (ET) between a pair of chromophores may take place efficiently over large distances (>10 Å) by the mediation of an intervening saturated hydrocarbon medium. For example, ET is found to take place on a sub-nanosecond timescale through saturated norbornylogous bridges greater than 13 Å in length, by a superexchange (through-bond coupling) mechanism. The dependence of the ET dynamics on the bridge length and configuration are consistent with the operation of a superexchange mechanism. The distinction between molecular wire behaviour and superexchange-mediated ET is made. The distance dependence of ET dynamics through different types of bridges—saturated and unsaturated hydrocarbon bridges, proteins, and duplex DNA—is discussed and explained. Strategies for prolonging the lifetimes of charge-separated states are explored and discussed. In general, long-lived charge-separated species have been generated using giant multichromophoric systems in which the charges are separated by large distances, often exceeding 20 Å. In contrast, it is shown that very long-lived charge-separated states, possessing the triplet multiplicity, may be generated using short ‘dwarf’ dyads, in which the charges are less than 6 Å apart. Charge recombination in these species is slowed by the difference in electron spin multiplicity between the charge-separated state and the ground state.