Assembling Di- and Polynuclear Cu(I) Complexes with Rigid Thioxanthone-Based Ligands: Structures, Reactivity, and Photoluminescence

Thioxanthone (TX) molecules and their derivatives are well-known photoactive compounds. Yet, there exist only a handful of luminescent systems combining TX with transition metals. Recently, we reported a TX-based PSP pincer ligand (L1) that appears as a promising platform for filling this niche. Herein, we demonstrate that with Cu(I) this ligand exclusively assembles into dimeric structures with either di- or polynuclear Cu(I) cores. With cationic Cu(I) precursors, complexes featuring solvent-bridged bis-cationic cores were obtained. These coordinatively unsaturated bimetallic systems showed surprisingly facile activation of the chloroform C-Cl bonds, suggesting a possible metal-metal cooperation. The reaction of L1 with binary Cu(I) halides afforded dimeric complexes with polynuclear [CuX]_n (n = 3 or 4) cores. With X = Br or I, emissive complexes containing stairstep [CuX]₄ clusters were obtained. Emission lifetimes in the microsecond range measured for these complexes were indicative of a triplet emission (phosphorescence), which according to our time-dependent density functional theory study originates from a halide-metal-to-ligand charge transfer between the [CuX]₄ cluster and the TX backbone of L1. Finally, the distinctive polynucleating behavior of L1 toward Cu(I) was also showcased by a comparison to another PSP ligand with a diaryl thioether backbone (L2), which formed only mononuclear pincer-type complexes, lacking any unusual reactivity or photoluminescence.