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

Abstract

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.

Combining Theory and Experiment to Get Insight into the Amorphous Phase of Luminescent Mechanochromic Copper Iodide Clusters

“…The calculations allow the reproduction of phosphorescence spectra and the thermochromic behavior that is unprecedented for [Cu 4 I 4 L 4 ] clusters and was rarely performed on high-nuclearity systems. 61…”

“…The thermochromism can thus be completely interpreted, and its two-excited-state origin is confirmed. The calculations allow the reproduction of phosphorescence spectra and the thermochromic behavior that is unprecedented for [Cu 4 I 4 L 4 ] clusters and was rarely performed on high-nuclearity systems …”

Structural and Spectroscopic Investigations of Two [Cu4X6]2– (X = Cl–, Br–) Clusters: A Joint Theoretical and Experimental Work

“…The simulated shortest wavelength is in very good agreement whereas the highest one is only in reasonable agreement. Indeed, the energy deviation for this lowest energy emission band is around 0.40 eV, which is larger than the usual standard for transition metal complexes. − However, with clusters the deviation seems to be larger . As a matter of fact, the optimized cluster possesses the same geometry as cluster 2 .…”

“…61−63 However, with clusters the deviation seems to be larger. 64 As a matter of fact, the optimized cluster possesses the same geometry as cluster 2. 35 Finally, as demonstrated in Figure 6, the second transition is red-shifted when the temperature decreases.…”

A Heptanuclear Copper Iodide Nanocluster

“…1 presents a large molecular structure with a great number of atoms (278). Calculations of both the ground and excited states on molecular compounds of such large size have rarely been conducted and especially on polymetallic systems . The geometries of the singlet ground state (S 0 ) and of the lowest excited triplet state (T 1 ) of 1 have thus been optimized.…”