Encapsulating Iodine and Copper into Copper(I) Clusters Stabilized by Dichalcogenolate Ligands: Stability, Structure, and Optical Properties.

The stability of large ligated copper(I) clusters of undeca- and dodecanuclearity encapsulating iodide and stabilized by dithio- and diseleno-phosph(in)ates was investigated by density functional theory (DFT) calculations. A bonding analysis is provided, which shows strong iono-covalent bonding between the iodide and its host. The electronic structures of the title compounds suggest the possibility for interesting photoluminescent properties, which were fully investigated by time-dependent DFT calculations including vibronic contributions to simulate the phosphorescence spectra. The quantum mechanical results were compared to the experimental data obtained for the new clusters [Cu(μ-I)(μ-I){SeP(OPr)}] and [Cu(μ-I)(μ-I)(SePPh)], whose syntheses, X-ray structures, and full characterizations are reported in this paper. From this combined theoretical/experimental investigation, it is suggested that the encapsulation by the same copper(I) cages of a formally Cu anion is also possible. DFT calculations on these species are consistent with the existence of stable two-electron superatoms.