| Summary: | Cyclic trinuclear complexes with group 11 metal(I) ions are fascinating and important to coordination chemistry. One of the ligands known to form these cyclic trinuclear complexes is pyrazolate, which is a bridging ligand that coordinates many transition metal ions in a Npz–M–Npz linear mode (Npz = pyrazolyl nitrogen atom). In these group 11 metal(I) ions, copper is the most abundant metal. Therefore, polynuclear copper(I) complexes are very important in this field. The cyclic trinuclear copper(I) complex <b>[Cu(3,5-Ph<sub>2</sub>pz)]<sub>3</sub></b> (3,5-Ph<sub>2</sub>pz<sup>–</sup> = 3,5-diphenyl-1-pyrazolate anion) was reported in 1988 as a landmark complex, but its photoluminescence properties have hitherto not been described. In this study, we report the photoluminescence and two different polymorphs of <b>[Cu(3,5-Ph<sub>2</sub>pz)]<sub>3</sub></b> and its derivative [<b>Cu(3-Me-5-Phpz)]<sub>3</sub></b> (3-Me-5-Phpz<sup>–</sup> = 3-metyl-5-phenyl-1-pyrazale anion). The substituents in <b>[Cu(3-Me-5-Phpz)]<sub>3</sub></b> cause smaller distortions in the solid-state structure and a red-shift in photoluminescence due to the presence of intermolecular cuprophilic interactions.
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