Photoelectromagnetic Responsive Adaptive Porous Frameworks through Dynamic Covalent Chemistry of Tetraarylethylene-backboned Aryldicyanomethyl Radicals

Angew Chem Int Ed Engl. 2023 May 22;62(22):e202301719. doi: 10.1002/anie.202301719. Epub 2023 Apr 20.

Abstract

Dynamic materials undergoing adaptive solid-state transitions are attractive for soft mechanics and information technology. Here, we report a novel porous framework system based on macrocyclic trimers assembled from open-shell tetraarylethylene building blocks with aryldicyanomethyl radicals as coupling linkers. Under mechanical, thermal, or chemical stimuli, the framework showed adaptability by activating conformational dynamics and radical-based transformations, thus displaying macroscopic responsiveness in terms of light absorption, luminescence, and magnetism. We studied the dynamic processes by variable-temperature nuclear magnetic resonance (VT-NMR), variable-temperature electron spin resonance (VT-ESR), and superconducting quantum interference device (SQUID) measurement and further established a proof-of-concept application for multi-modal information encryption. The strategy may open avenues for rational design of solid-state photoelectromagnetic dynamic materials by merging dynamic covalent coupling chemistry and functional aggregation principles.

Keywords: Dynamic Covalent Chemistry; Porous Molecular Material; Radical.