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

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posted on 31.10.2017, 13:21 by Camille Latouche, Jian-Hong Liao, Yi-Juan Li, Ruei-Yi Shiu, Vincenzo Barone, Samia Kahlal, C. W. Liu, Jean-Yves Saillard
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 [Cu119-I)­(μ3-I)3­{Se2P­(OiPr)2}6]+ and [Cu119-I)­(μ3-I)3­(Se2PPh2)6]+, 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.