From chain to framework: atomically precise silver cluster-assembled architectures

Abstract

The controlled assembly of atomically defined metal nanoclusters (NCs) into extended frameworks represents a powerful approach to developing functional materials with tailored properties. However, achieving structural dimensionality (1D–3D) control while maintaining the integrity of a single cluster core remains a significant challenge. Herein, we report the construction of a series of silver cluster-assembled materials (SCAMs) using Ag₁₂ clusters and directional N-donor ligands of varying lengths. The resulting architectures—1D [Ag₁₂(S^tBu)₆(CF₃COO)₆(Py₂S)₂(CH₃CN)₂], 2D [Ag₁₂(S^tBu)₆(CF₃COO)₆(bpm)₃], and 3D [Ag₁₂(S^tBu)₆(CF₃COO)₆(tmdp)₃]—feature preserved cuboctahedral Ag₁₂ cores connected through directional Ag-N bonding. Single-crystal X-ray diffraction confirms structural fidelity across all dimensions. These assemblies provide a rare platform to systematically explore the impact of dimensionality on function. Catalytic tests reveal that all three SCAMs efficiently catalyze the hydrogenation of nitroaromatics to aminoaromatics, with the 1D SCAM exhibiting the highest activity. This work highlights a rational, ligand-directed strategy for creating dimensionally tunable, atomically precise cluster-based frameworks and establishes a direct link between structural dimensionality and catalytic performance. Our findings offer a blueprint for designing next-generation nanomaterials with customized architectures and functions for advanced catalytic and optoelectronic applications.