Steric-hindrance-directed Growth of Perylene Diimide-based Two-dimensional Coordination Polymer Nanosheets for Photocatalysis

Abstract

For two-dimensional nanomaterials based on large π-conjugated ligands, the intrinsic tendency toward strong π–π interactions often drives isotropic stacking, which thermodynamically favors the formation of three-dimensional bulk architectures rather than extended two-dimensional sheets. Therefore, developing organic ligands with large π conjugation still presents significant challenges. Here, we design the perylene diimide (PDI) ligand by introducing bulky alkyl chains and vertically arranged terpyridine units, effectively suppressing excessive π–π stacking while promoting plane-coordination-directed growth. A two-dimensional PDI-based coordination polymer nanosheet (NS) is constructed at the liquid–liquid interface via steric hindrance modulation. The resulting ultrathin NSs could be used as photocatalysts for photocatalytic oxidation of benzylamine and thioanisole with high conversion rates and selectivity under mild conditions.