Dimensional Control and Optical Properties of Tunable Silver Coordination Polymers via Nanocluster Assembly

The controlled assembly of silver nanoclusters (NCs) into tunable coordination polymers (CPs) presents opportunities for functional material design, although stability-related challenges persist. Herein, we report the synthesis of three silver CPs (<b>1</b>-<b>3</b>) by adjusting reaction conditions, such as method and solvent, facilitating the self-assembly of silver NCs with the 4,8-ethenobenzo[1,2-<i>c</i>:4,5-<i>c</i>'] dipyrrole-1,3,5,7(2<i>H</i>,6<i>H</i>)-tetrone (BDI) ligand. Single crystal X-ray diffraction analyses reveal three distinct architectures: a one-dimensional cyclic loop chain (<b>1</b>), a two-dimensional layered structure (<b>2</b>), and a 2-fold interpenetrated cyclic loop chain (<b>3</b>). We systematically explore the hydrogen bonding interactions, structural stability, and optical properties of these materials, demonstrating that the spatial arrangement of silver NCs and BDI ligands dictates both the dimensionality and the photophysical behavior. This study provides new insights into the design of silver-based CPs with enhanced optical properties and paves the way for advanced applications in optoelectronics and molecular sensing.