Enabling Rotated Stacking Displacement in Two‐Dimensional Covalent Organic Frameworks via Interlayer Electrostatic Repulsion

ABSTRACT Tuning the interlayer stacking in 2D covalent organic frameworks (2D COFs) allows unique structural and optoelectronic properties. However, the diversity of 2D COF stacking modes is limited to eclipsed, serrated, and shifted stacking. In this study, we develop a method for constructing COFs with rotated stacking by modulating interlayer electrostatic repulsion. COFs with rotated or eclipsed (AA) stacking are obtained via reactions between triamine and dialdehyde monomers with or without pyridinium substituents. Importantly, the modulation of pyridinium substituents enables the transformation of different stacking modes, as well as the conversion of amorphous to crystalline materials. Moreover, multicomponent‐based stacking regulation strategies are found to efficiently mediate photocatalytic hydrogen peroxide production, owing to their tunable photophysical properties. Our findings provide perspectives on leveraging interlayer repulsion to tailor interlayer stacking in 2D COFs, thereby diversifying their topologies and improving their optoelectronic properties.