Steric Hindrance Governs the Photoinduced Structural Planarization of Cycloparaphenylene Materials.

Cycloparaphenylenes ([]CPPs) and their derivatives are known for the unique size-dependent photophysical properties, which are largely attributed to the structural planarization-associated exciton localization, attracting substantial research attention. In this work, we show that the steric hindrance between neighboring structural units plays a key role in governing the photoinduced global/local structural planarization and electron-hole distribution features of []CPP materials, due to the tunable strength of H···H repulsion between neighboring units via structural modification or C-H distance variation as revealed by density functional theory (DFT) and time-dependent DFT calculations. According to our results, steric hindrance controls the manner and also the extent of excited-state structural planarization, where a weak (strong) steric hindrance favors (hinders) structural planarization upon relaxation in the first excited singlet (S) state as compared to the ground (S)-state structure. Depending on the molecular structures, steric hindrance leads to fully delocalized, partially separated, or more localized electron-hole distributions. For example, via H···H repulsion release by manually shortening the C-H distance or by chemical substitution of C-H with N atoms, the modified [10]CPP structures show fully planarized configurations (each dihedral angle can be less than 2°) and entirely delocalized electron-hole distribution upon photorelaxation. This work provides insights into the structural origin of the unusual photophysical properties of []CPPs and shows the promise of steric hindrance tuning in accessing diverse excited-state features in []CPP materials.