Catalyst‐ and Solvent‐Free Synthesis of a Chemically Stable Aza‐Bridged Bis(phenanthroline) Macrocycle‐Linked Covalent Organic Framework

Abstract

Developing new linkage-based covalent organic frameworks (COFs) is one of the major topics in reticular chemistry.E lectrically conductive COFs have enabled applications in energy storage and electrochemical catalysis,w hich are not feasible using insulating COFs.D espite significant advances,t he construction of chemically stable conductive COFs by the formation of new linkages remains relatively unexplored and challenging. Here we report the solvent-and catalyst-free synthesis of at wo-dimensional aza-bridged bis(phenanthroline) macrocycle-linked COF (ABBPM-COF) from the thermally induced poly-condensation of at ri-topic monomer and ammonia gas.The ABBPM-COF structure was elucidated using multiple techniques,i ncluding X-rayd iffraction analysis combined with structural simulation, revealing its crystalline nature with an ABC stackingmode.Further experiments demonstrated its excellent chemical stability in acid/base solutions.E lectrical-conductivity measurements showed that the insulating ABBPM-COF becomes as emiconducting material after exposure to iodine vapor.