ic7b02269_si_002.txt (53.33 kB)
Encapsulating Iodine and Copper into Copper(I) Clusters Stabilized by Dichalcogenolate Ligands: Stability, Structure, and Optical Properties
dataset
posted on 2017-10-31, 13:21 authored by Camille Latouche, Jian-Hong Liao, Yi-Juan Li, Ruei-Yi Shiu, Vincenzo Barone, Samia Kahlal, C. W. Liu, Jean-Yves SaillardThe 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 [Cu11(μ9-I)(μ3-I)3{Se2P(OiPr)2}6]+ and [Cu11(μ9-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.