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.