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

Xinhao Wang, Hui Zhang, Haohao Liu, Gaoqiang Xu, Weiming Lai, Yang Zhang, Xinlong Ni, Sheng Xie, Ben Zhong Tang, Zebing Zeng

2023Angewandte Chemie International Edition26 citationsDOIOpen Access PDF

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.

Topics & Concepts

Electron paramagnetic resonanceCovalent bondMagnetismRadicalSquidCoupling (piping)ChemistryMaterials sciencePorosityChemical physicsNanotechnologyCondensed matter physicsPhysicsNuclear magnetic resonanceOrganic chemistryMetallurgyEcologyBiologyCovalent Organic Framework ApplicationsLuminescence and Fluorescent MaterialsConducting polymers and applications