Phenothiazine-based covalent organic frameworks with low exciton binding energies for photocatalysis

Designing delocalized excitons with low binding energy (E-b) in organic semiconductors is urgently required for efficient photochemistry because the excitons in most organic materials are localized with a high E-b of >300 meV. In this work, we report the achievement of a low E-b of similar to 50 meV by constructing phenothiazine-based covalent organic frameworks (COFs) with inherent crystallinity, porosity, chemical robustness, and feasibility of bandgap engineering. The low E-b facilitates effective exciton dissociation and thus promotes photocatalysis by using these COFs. As a demonstration, we subject these COFs to photocatalytic polymerization to synthesize polymers with remarkably high molecular weight without any requirement of the metal catalyst. Our results can facilitate the rational design of porous materials with low E-b for efficient photocatalysis.

Automated summary

In this work, phenothiazine-based covalent organic frameworks (COFs) with low binding energy excitons were successfully designed, and their photocatalytic properties were demonstrated by synthesizing high molecular weight polymers without using metal catalysts.