Diversifying Single‐Crystal Structures of Covalent Organic Polymers Through a Symmetry‐Broken Strategy

Abstract

ABSTRACT Recently, growing single crystals of covalent organic polymers (COPs) through dative B←N bonds has been proven to be a promising strategy. Despite these developments, constructing diverse COP structures using identical structural motifs to investigate the variations in their performance remains a significant but challenging task. In this paper, we introduce a strategy aimed at reducing the symmetry of structural units to achieve this target. By employing the 3‐pyridyl‐based tetrathiafulvalene motif (labeled as TTF‐(3‐py) 4 ), a series of single‐crystal COP structures sharing the same motifs, including one‐dimensional (1D) zigzag chains ( CityU‐61 ), 1D nanobelt ( CityU‐62 ), and 2D layer ( CityU‐63 ) structures, are constructed under different solvent conditions. The rotatability of the carbon‐carbon single bond, coupled with the deviation of nitrogen in pyridine from the symmetry axis, endows TTF‐(3‐py) 4 with a diverse range of configurations. These COP compounds exhibit excellent light absorption properties and redox activities, facilitating efficient photocatalytic synthesis of hydrogen peroxide (H 2 O 2 ) from water and air. Notably, CityU‐63 exhibits the highest catalytic activity, with an H 2 O 2 production rate of 10 488.9 µmol g −1 h −1 , positioning it among the most effective photocatalysts currently employed for H 2 O 2 photosynthesis.