Exploiting singlet excited state conformation for rational design of highly efficient photoinduced electron transfer molecules

In spite of the pivotal role of excited state electronic structures as regulation of photoinduced electron transfer (PET) process, the effect of excited state conformation on PET remains elusive. Here we exploit distinguishable emission characters of trans and cis singlet excited states of donor-acceptor-donor ensemble MTPAAZO to reveal that its PET efficiency and rate are closely depended on its singlet excited state conformation. The PET process occurs solely in cis conformation of MTPAAZO singlet excited states. Novel molecule (MTPA)2Ab as-designed with similar structure of MTPAAZO cis singlet excited states shows high PET efficacy and rate, leading to long-lived CS states. Our findings enable the rational design of the novel molecules with highly efficient PET process suitable for charge separation applications. [Display omitted] •Different fluorescence emission features from the trans and cis singlet excited states were identified.•Cis→trans conversion in ground states and trans→cis isomerization in singlet excited states were discovered.•The PET process was observed only in cis conformation of MTPAAZO singlet excited states.