Abstract
Here we report three zero-dimensional (0-D) copper cluster structures, (2-TTPS)[CuCl2] (1), (2-TTPS)2[Cu4Br6] (2), and (2-TTPS)4[Cu4I8] (3), formed by self-assembly of the 2-TTPSX ligand (2-TTPSX = triphenyl(thiophen-2-yl)phosphonium chloride/bromide/iodide) with neutral CuCl/CuBr/CuI, respectively. The CuX salts exhibit a propensity to form high nuclearity aggregates or clusters, leading to a specific structural richness. In 1, two [CuCl2]− units are staggered along the c-axis. In 2, the larger [Cu4Br6]2− inorganic unit is completely encapsulated by 2-TTPS+ cations, with each Cu+ located at the center of a [CuBr4]3− tetrahedral structure. The copper cluster in 3 is characterized by an unprecedented, centrosymmetric tetramer formation. The variation in copper cluster types is achieved through the control of a single crystal growth technique using different CuX salts for assembly. This work introduces the synthetic methods, crystallographic features, and optical properties of the three materials.
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