Charge-Separation and Charge-Recombination Rate Constants in a Donor–Acceptor Buckybowl-Based Supramolecular Complex: Multistate and Solvent Effects

[Image: see text] The kinetics of the nonradiative photoinduced processes (charge-separation and charge-recombination) experimented in solution by a supramolecular complex formed by an electron-donating bowl-shaped truxene-tetrathiafulvalene (truxTTF) derivative and an electron-accepting fullerene fragment (hemifullerene, C(30)H(12)) has been theoretically investigated. The truxTTF·C(30)H(12) heterodimer shows a complex decay mechanism after photoexcitation with the participation of several low-lying excited states of different nature (local and charge-transfer excitations) all close in energy. In this scenario, the absolute rate constants for all of the plausible charge-separation (CS) and charge-recombination (CR) channels have been successfully estimated using the Marcus–Levich–Jortner (MLJ) rate expression, electronic structure calculations, and a multistate diabatization method. The outcomes suggest that for a reasonable estimate of the CS and CR rate constants, it is necessary to include the following: (i) optimally tuned long-range (LC) corrected density functionals, to predict a correct energy ordering of the low-lying excited states; (ii) multistate effects, to account for the electronic couplings; and (iii) environmental solvent effects, to provide a proper stabilization of the charge-transfer excited states and accurate external reorganization energies. The predicted rate constants have been incorporated in a simple but insightful kinetic model that allows estimating global CS and CR rate constants in line with the most generalized three-state model used for the CS and CR processes. The values computed for the global CS and CR rates of the donor–acceptor truxTTF·C(30)H(12) supramolecular complex are found to be in good agreement with the experimental values.