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Increased Charge Separation Rates with Increasing Donor-Acceptor Distance in Molecular Triads: the Effect of Solvent Polarity

Luo, Yusen; Barthelmes, Kevin; Wächtler, Maria; Winter, Andreas; Schubert, Ulrich S.; Dietzek, Benjamin
in: Journal of Physical Chemistry C (2017) 9220

Distance-dependent electron transfer in donor–spacer–acceptor systems is accepted to occur via two distinct mechanisms, that is, by coherent superexchange or incoherent hopping. In general, the rate of electron transfer (kET) decreases with increasing donor–acceptor distances, irrespective of the actual mechanism being responsible for the process. However, recently Wenger and his group showed that in the frame of the superexchange mechanism electron-transfer rates can pass a maximum when increasing the transfer distance. This manuscript presents an investigation of the forward electron transfer in a series of donor (N-methylphenothiazine)–photocenter (Ru(II) bis(terpyridine) complex)–acceptor (N-methylfulleropyrrolidine) triads that reveals the control of the electron-transfer rates by solvent variation to an extent that in acetonitrile an increasing electron-transfer rate is observed with increasing donor–acceptor distance, while in dichloromethane an increase in the separation causes the electron transfer rate to drop. This behavior is qualitatively rationalized based on a recently introduced model. Nonetheless, the quantitative mismatch between the results presented here and the theory indicates that nonexponential distance-dependent couplings will have to be considered in extending the theory.

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