Non-Equilibrium Assembly of Atomically-Precise Copper Nanoclusters.

Accurate structure control in dissipative assemblies is vital for precise biological functions. However, the accuracy and functionality of current artificial dissipative assembly are far from this objective. Herein, we introduce a novel approach by harnessing complex chemical reaction networks (CRN) rooted in coordination chemistry to create well-defined dissipative assemblies. We designed atomically-precise Cu nanocluster (CuNCs), specifically Cu 11 (μ 9 -Cl)(μ 3 -Cl) 3 L 6 Cl clusters (L = 4-methyl-piperazine-1-carbodithioate). Cu(I)-ligand ratio change and dynamic Cu(I)-Cu(I) metallophilic/coordination interactions enable the reorganization of CuNCs into metastable CuL 2 , finally converting into the equilibrium [CuL·Y]Cl complexes (Y = MeCN or H 2 O) via Cu(I) oxidation/reorganization and ligand exchange process. Upon adding fuels (ascorbic acid, AA), the system goes further dissipative cycles. We observed that the encapsulated/bridging halide ions exert a subtle influence on the optical properties of CuNCs and topological changes of polymeric networks when integrating CuNCs as crosslink sites. CuNCs duration and switch period could be controlled by varying the ions, AA concentration, O 2 pressure and pH. The unique Cu(I)-Cu(I) metallophilic and coordination interactions provide a versatile toolbox for designing delicate life-like materials, paving the way for tailored dissipative assemblies with precise structures and functionalities. Furthermore, these CuNCs can be employed as modular units within polymers for materials mechanics or functionalization studies, expanding their potential applications. This article is protected by copyright. All rights reserved.