Switching Competition between Electron and Energy Transfers in Porphyrin–Fullerene Dyads

Porphyrin-fullerene dyads were intensively studied as molecular donor-acceptor systems providing efficient photoinduced charge separation (CS). A practical advantage of the dyads is the possibility to tune its CS process by the porphyrin periphery modification, which allows us to optimize the dyad for particular applications. However, this tuning process is typically composed of a series of trial stages involving the development of complex synthetic schemes. To address the issue, we synthesized a series of dyads with properties switching between electron and energy transfer in both polar (benzonitrile) and non-polar (toluene) media, and developed a computation procedure with sufficient reliability by which we can predict the CS properties of the dyad in different media and design new dyads. The dyads photochemistry was established by conducting ultrafast transient absorption study in toluene, anisole and benzonitrile. The most crucial step in computational modelling was to establish a procedure for the correction of the electronic-state energies obtained by DFT so that the effects of the electron correlation and the long range interactions are properly incorporated. We also carried out standard electrochemical measurements and show that our computation approach predicts better thermodynamics of the dyads in different solvents.