Redefining the Coordination Mode of 1,2,4‐Triazolylidene: Bridging the Gap Between Molecular Organometallic Chemistry and Extended Porous Architectures

Abstract Although molecular organometallic complexes are widely exercised across various chemistry domains, their evolution into extended porous frameworks has been lacking for C‐donor NHC ligands. In this study, we present the first such example by leveraging the rare coordination of the 1,2,4‐triazolylidene N2 site, embedded within a bis(NHC) ligand scaffold ( L1 ), in conjunction with flexible coordination mode of the Cu I ‐ion. Initially, the formation of discrete multinuclear Cu I ‐NHC complexes ( 2a , b ) was observed, as confirmed by extensive NMR analyses, which transformed into highly crystalline and porous extended framework ( 3b ) upon crystallization, marking the first report wherein the M─C NHC bonds play critical roles in governing the framework topology. The structural integrity and origin of stability was thoroughly investigated using a combination of detailed analytical and theoretical studies.