Theoretical description of photoinduced electron transfer in donor-acceptor supramolecular complexes based on carbon buckybowls

Herein, we explore, from a theoretical perspective, the nonradiative photoinduced processes (charge separation and energy transfer) within a family of donor-acceptor supramolecular complexes based on the electron-donor truxene-tetrathiafulvalene (truxTTF) derivative and a series of curved fullerene fragments (buckybowls) of different shapes and sizes (C30H12, C32H12, and C38H14) as electron acceptors that successfully combine with truxTTF via non-covalent interactions. The resulting supramolecular complexes (truxTTF·C30H12, truxTTF·C32H12, and truxTTF·C38H14) undergo charge-separation processes upon photoexcitation through charge-transfer states involving the donor and acceptor units. Despite the not so different size of the buckybowls, they present noticeable differences in the charge-separation efficiency owing to a complex decay post-photoexcitation mechanism involving several low-lying excited states of different natures (local and charge-transfer excitations), all closely spaced in energy. In this intricate scenario, we have adopted a theoretical approach combining electronic structure calculations at (time-dependent) density functional theory, a multistate multifragment diabatization method, the Marcus-Levitch-Jortner semiclassical rate expression, and a kinetic model to estimate the charge separation rate constants of the supramolecular heterodimers. Our outcomes highlight that the efficiency of the photoinduced charge-separation process increases with the extension of the buckybowl backbone. The supramolecular heterodimer with the largest buckybowl (truxTTF·C38H14) displays multiple and efficient electron-transfer pathways, providing a global photoinduced charge separation in the ultrafast time scale in line with the experimental findings. The study reported indicates that modifications in the shape and size of buckybowl systems can give rise to attractive novel acceptors for potential photovoltaic applications.