Interfacial Hydrogen‐Bond Interactions Driven Assembly toward Polychromatic Copper Nanoclusters

Abstract Constructing versatile metal nanoclusters (NCs) assemblies through noncovalent weak interactions between inter‐ligands is a long‐standing challenge in interfacial chemistry, while compelling interfacial hydrogen‐bond‐driven metal NCs assemblies remain unexplored so far. Here, the study reports an amination‐ligand o ‐phenylenediamine‐coordinated copper NCs (CuNCs), demonstrating the impact of interfacial hydrogen‐bonds (IHBs) motifs on the luminescent behaviors of metal NCs as the alteration of protic solvent. Experimental results supported by theoretical calculation unveil that the flexibility of interfacial ligand and the distance of cuprophilic Cu I ···Cu I interaction between intra‐/inter‐NCs can be tailored by manipulating the cooperation between the diverse IHBs motifs reconstruction, therewith the IHBs‐modulated fundamental structure‐property relationships are established. Importantly, by utilizing the IHBs‐mediated optical polychromatism of aminated CuNCs, portable visualization of humidity sensing test‐strips with fast response is successfully manufactured. This work not only provides further insights into exploring the interfacial chemistry of NCs based on inter‐ligands hydrogen‐bond interactions, but also offers a new opportunity to expand the practical application for optical sensing of metal NCs.