Controlling short- and long-range electron transfer processes in molecular dyads and triads

Novel it-extended tetrathiafulvalene (exTIFF)-based donor acceptor hybrids-dyads and triads-have been synthesized following a multistep synthetic procedure. Cyclic voltammetry and absorption spectroscopy, conducted in room temperature solutions, reveal features that are identical to the sum of the separate donor and acceptor moieties. Steady-state and time-resolved photolytic techniques confirm that upon photoexcitation of the fullerene chromophore, rapid (1.25 x 10(10) s(-1)) and efficient (67%) charge separation leads to long-lived, charge-separated radical pairs. Typical lifetimes for the dyad ensembles range between 54 and 460 ns, with the longer values found in more polar solvents. This indicates that the dynamics are located in the 'normal region' of the Marcus curve. In the triads, subsequent charge shifts transform the adjacent radical pair into the distant radical pair, for which we determined lifetimes of up to 111 mus in DMF-values never previously accomplished in molecular triads. In the final charge-separated state, large donor-acceptor separation (center-to-center distances: approximate to30 Angstrom) minimizes the coupling between reduced acceptor and oxidized donor. Analysis of the charge recombination kinetics shows that a stepwise mechanism accounts for the unusually long lifetimes.