Structural Dimensional Regulation in Organic Copper(I) Chloride Family based on Same Building Unit

Abstract Systematic dimensional regulation of low-dimensional metal halides remains challenging for establishing clear dimension–property relationships because changes in dimensionality are often accompanied by variations in chemical composition or inorganic building units. Herein, we realize systematic dimensionality regulation across 0D (DMP)2Cu2Cl6, 1D (DMP)Cu2Cl4, and 2D (DMP)Cu2Cl4 through a solvent-mediated structural engineering strategy, while preserving the same organic cation and local [Cu2Cl6] dimer building unit. This homologous series enables a more direct correlation between framework connectivity and structural and photophysical properties, including Cu···Cu contacts, band gaps, and photoluminescence associated with self-trapped excitons. The three compounds exhibit distinct Cu···Cu contacts and emission profiles, highlighting the influence of structural dimensionality and local coordination environments on their photoluminescence behavior.