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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.

International audienceTwo luminescent, monoanionic chalcogenide-centered nonanuclear silver clusters stabilized by dichalcogenophosphates were synthesized and fully characterized by various spectroscopies including multinuclear NMR and ESI-mass. Single crystal X-ray diffraction studies on both cluster anions, [Ag9(S)_S2P(OEt)2₈]−, 1, and [Ag9(Se)_Se2P(OEt)2₈]−, 2, reveal that the nine silver atoms form an extremely distorted tricapped trigonal prism, which has an encapsulating chalcogenide. The coordination geometry of the central chalcogenide appears to be monocapped trigonal prismatic, which was analyzed by DFT calculations. The origin of the yellow emission is assigned by TDDFT calculations to originate from a chalcogen (ligand + encapsulated) → silver charge transfer. © 2016, Springer Science+Business Media New York