Quantum Dynamics of Charge Carriers in Fullerenes Encapsulated by Covalent Organic Polyhedra: Choice of Fullerene Matters

Charge separation is at the heart of solar energy applications, and efficient materials require fast photoinduced electron transfer (ET) and slow charge recombination (CR). Using time-dependent self-consistent charge density functional tight-binding theory combined with nonadiabatic (NA) molecular dynamics, we report a detailed analysis of ET and CR in hybrids composed of photoactive covalent organic polyhedra (COP) and encapsulated fullerenes. The ET occurs on a subpicosecond time scale and accelerates with increasing fullerene diameter, C₆₀ to C₇₀ to C₈₄. As the fullerene size increases, the π-electron system available for interaction with the COP grows, the fullerene-COP separation decreases, and the number of fullerene states available to accept the photoexcited electron increases, accelerating the ET. In comparison, the CR occurs on a nanosecond time scale and correlates with the length of the fullerene shortest axis because the relevant fullerene state is polarized in that direction. The largest and least symmetrical C₈₄ exhibits the fastest ET and the slowest CR, making COP@C₈₄ the most promising hybrid. Both high-frequency bond stretching and bending vibrations and low-frequency breathing modes are involved in the ET and CR processes, with more modes present in the C₈₄ system due its lower symmetry. The 10-20 fs vibrationally induced coherence loss in the electronic subsystem contributes to long lifetimes of the charge-separated states. The comprehensive investigation of the structure-property relationship of the charge carrier dynamics in the COP@fullerene hybrids provides a detailed atomistic understanding of interfacial ET processes and generates guidelines for rational design of high-performance materials for solar energy and related applications.