Metal Effect on the Supramolecular Structure, Photophysics, and Acid−Base Character of Trinuclear Pyrazolato Coinage Metal Complexes

Varying the coinage metal in cyclic trinuclear pyrazolate complexes is found to significantly affect the solid-state packing, photophysics, and acid−base properties. The three isoleptic compounds used in this study are {[3,5-(CF3)2Pz]M}3 with M = Cu, Ag, and Au (i.e., Cu3, Ag3, and Au3, respectively). They form isomorphous crystals and exist as trimers featuring nine-membered M3N6 rings with linear two-coordinate metal sites. On the basis of the M−N distances, the covalent radii of two-coordinate CuI, AgI, and AuI were estimated as 1.11, 1.34, and 1.25 Å, respectively. The cyclic {[3,5-(CF3)2Pz]M}3 complexes pack as infinite chains of trimers with a greater number of pairwise intertrimer M···M interactions upon proceeding to heavier coinage metals. However, the intertrimer distances are conspicuously short in Ag3 (3.204 Å) versus Au3 (3.885 Å) or Cu3 (3.813 Å) despite the significantly larger covalent radius of AgI. Remarkable luminescence properties are found for the three M3 complexes, as manifested by the appearance of multiple unstructured phosphorescence bands whose colors and lifetimes change qualitatively upon varying the coinage metal and temperature. The multiple emissions are assigned to different phosphorescent excimeric states that exhibit enhanced M···M bonding relative to the ground state. The startling luminescence thermochromic changes in crystals of each compound are related to relaxation between the different phosphorescent excimers. The trend in the lowest energy phosphorescence band follows the relative triplet energy of the three MI atomic ions. DFT calculations indicate that {[3,5-(R)2Pz]M}3 trimers with R = H or Me are bases with the relative basicity order Ag ≪ Cu < Au while fluorination (R = CF3) renders even the Au trimer acidic. These predictions were substantiated experimentally by the isolation of the first acid−base adduct, {[Au3]2:toluene}, in which a trinuclear AuI complex acts as an acid.