Abstract
Understanding the dynamics of the back electron transfer (BET) rate of ion pairs from the electronically excited state of donor-acceptor systems is crucial for developing materials for organic electronics. The structure-property relationships in the organic molecular architectures play a key role in controlling the BET rate and have been utilized as a criterion to design systems with a reduced BET rate. Here, we examine the influence of isomerism on the BET rate in anthracene based systems, viz., (E)-2-(2-(anthracen-9-yl)vinyl)benzonitrile (ortho-CN) and (E)-3-(2-(anthracen-9-yl)vinyl)benzonitrile (meta-CN) with N,N-diethylaniline (DEA) in methylcyclohexane using time-resolved spectroscopy. The radical cation (DEA˙+) and the radical anion (ortho-CN˙- or meta-CN˙-) generated after photoexcitation show synchronous decay kinetics, and the rate constant of back electron transfer (kBET) for the DEA/ortho-CN pair was 6.6 × 104 s-1, which is ca. 2 orders of magnitude lower compared with the DEA/meta-CN pair. The role of isomerism in providing resonance stabilization for the organic radicals is expected to have implications for strategies that retard charge recombination in photovoltaics. The role of the molecular structural features that dictate the kinetics for charge recombination has been further identified using quantum calculations.
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