Stimulus‐Responsive Organometallic Assemblies Based on Azobenzene‐Functionalized Poly‐NHC Ligands

Abstract The reversible photoisomerization of azobenzene (AZB) and its derivatives has been applied across various fields. Developing discrete AZB‐functionalized organometallic cages is essential for manufacturing functional materials. In this work, we designed and fabricated a series of three‐dimensional, hexaazobenzene‐terminated poly‐NHC‐based (NHC= N ‐heterocyclic carbene) complexes [M 3 ( A ) 2 ](BF 4 ) 3 and [M 3 ( B ) 2 ](BF 4 ) 3 (M = Ag, Au). In the newly prepared M I ‐C NHC assemblies, these peripheral AZB units linked to the central backbones can undergo efficient and recyclable isomerization upon external stimulation, effectively creating a switchable organometallic assembly system. Compared to the NHC precursor, the metalized framework demonstrates higher isomerization efficiency, thereby establishing a foundation for the subsequent application of AZB‐functionalized M I ‐C NHC assemblies.