Trinuclear Copper(I) and Silver(I) Complexes of a Pentafluorosulfanyl-Decorated Pyrazolate

This study reports the synthesis and characterization of the first fluorinated coinage metal pyrazolates with SF₅ groups, specifically {[3-(SF₅)Pz]M}₃ (M = Cu, Ag), and compares them to trifluoromethylated analogs. X-ray analysis reveals different pyrazolyl ligand orientations and metallophilic interactions, as well as supramolecular structures influenced by fluorinated substituents and metals. The {[3-(SF₅)Pz]M}₃ complexes form face-to-face sandwich adducts with benzene. Photophysical investigations show that copper complexes exhibit long-lived phosphorescence, while silver analogs display fast fluorescence, with emission properties modulated by substituents, solvent environment, and intermolecular interactions. Computational studies confirm the experimental geometries and demonstrate that SF₅ substituents increase the π-acidity and enhance arene binding over the analogs featuring the smaller and less-electron-withdrawing CF₃ groups and provide insights into metallophilic interactions and photoluminescence. These newly uncovered SF₅ decorated materials, with enhanced π-acidity and arene-binding ability, are promising materials for molecular sensing and tunable luminescence.