Conformational and Solvent Effects on the Photoinduced Electron Transfer Dynamics of a Zinc Phthalocyanine–Benzoperylenetriimide Conjugate: A Nonadiabatic Dynamics Simulation

Abstract Herein, we employed a combination of static electronic structure calculations and nonadiabatic dynamics simulations at linear‐response time dependent density functional theory (LR‐TDDFT) level with the optimally tuned range‐separated hybrid (OT‐RSH) functional to explore the ultrafast photoinduced dynamics of a zinc phthalocyanine‐benzoperylenetriimide (ZnPc‐BPTI) conjugate. Due to the flexibility of the linker, we identified two major conformations: the stacked conformation (ZnPc‐BPTI‐1) and the extended conformation (ZnPc‐BPTI‐2). Since the charge transfer states are much lower than the lowest local excitation in ZnPc‐BPTI‐1, which is contrary to ZnPc‐BPTI‐2, the ultrafast electron transfer (~3.6 ps) is only observed in the nonadiabatic simulations of ZnPc‐BPTI‐1 upon local excitation around the absorption maximum of ZnPc. However, when considering the solvent effects in benzonitrile: the lowest S 1 states are both charge transfer states from ZnPc to BPTI for different conformers. Subsequent nonadiabatic dynamics simulations indicate that both conformers experience ultrafast electron transfer in benzonitrile with two time constants of 90 [100] fs and 1.40 [1.43] ps. Our present work not only agrees well with previous experimental study, but also points out the important role of conformational changes and solvent effects in regulating the photodynamics of organic donor‐acceptor conjugates.