Non-Equilibrium Assembly of Atomically-Precise Copper Nanoclusters.
basic_science · Level V
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- Record sourced from PubMed, PMID 38294175.
- Also identified by DOI 10.1002/adma.202311818.
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Abstract
Accurate structure control in dissipative assemblies (DSAs) is vital for precise biological functions. However, accuracy and functionality of artificial DSAs are far from this objective. Herein, a novel approach is introduced by harnessing complex chemical reaction networks rooted in coordination chemistry to create atomically-precise copper nanoclusters (CuNCs), specifically Cu<sub>11</sub>(µ<sub>9</sub>-Cl)(µ<sub>3</sub>-Cl)<sub>3</sub>L<sub>6</sub>Cl (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<sub>2</sub>, finally converting into equilibrium [CuL·Y]Cl (Y = MeCN/H<sub>2</sub>O) via Cu(I) oxidation/reorganization and ligand exchange process. Upon adding ascorbic acid (AA), the system goes further dissipative cycles. It is observed that the encapsulated/bridging halide ions exert subtle influence on the optical properties of CuNCs and topological changes of polymeric networks when integrating CuNCs as crosslink sites. CuNCs duration/switch period could be controlled by varying the ions, AA concentration, O<sub>2</sub> pressure and pH. Cu(I)-Cu(I) metallophilic and coordination interactions provide a versatile toolbox for designing delicate life-like materials, paving the way for DSAs with precise structures and functionalities. Furthermore, CuNCs can be employed as modular units within polymers for materials mechanics or functionalization studies.