Modulation of the 1D/2D Dimensionality by Ligand Exchange in a Series of Cu- and Ag-Naphthalenethiolate Coordination Polymers: Effect on Conductivity and Photoemission.

Metal-organic chalcogenolates (MOCs) are an expanding family of coordination polymers that have attracted increasing interest from both chemists and physicists due to their intriguing physical properties, including intense and tunable photoemission, semiconducting behavior, and strong light-matter interactions. These materials are typically composed of a soft metal center, most often 10 coinage metals, coordinated to soft chalcogenolate ligands such as thiolates or selenolates, and they frequently form one- or two-dimensional (1D/2D) networks. However, the limited number of reported MOCs and the lack of systematic studies hinder a clear understanding of structure-property relationships. In this work, we investigate the influence of ligand functionalization and structural dimensionality on the physical properties of MOCs through the synthesis and the structural determination from powder X-ray diffraction data of four new coordination polymers based on Cu-(I) and Ag-(I) with 1- and 2-naphthalenethiolate ligands (1-NT and 2-NT). The 1-NT ligand leads to 1D structures, whereas 2-NT gives rise to 2D networks. Photophysical and electrical measurements reveal that [Cu-(1-NT)] exhibits both the highest quantum yield and the highest electrical conductivity among the series. These results highlight the combined influence of the metal center (Cu vs Ag) and structural dimensionality (1D vs 2D) in designing efficient MOC-based materials.