Exploring the nature of the excitation energies in [Re6(μ3-Q8)X6]4− clusters: a relativistic approach

Rabanal‐León, Walter A.; Murillo-López, Juliana A.; Páez‐Hernández, Dayán; Arratia‐Pérez, Ramiro

doi:10.1039/c5cp02003d

Cited by 7 publications

(1 citation statement)

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“…Studies of the electronic structure of octahedral clusters have shown that cluster core is a structural unit with delocalized molecular orbitals, e.g., their frontier molecular orbitals consist of atomic orbitals of the metal atoms and inner ligands. 5 At the same time, the cluster core is formed in the high-temperature synthesis and is a robust unit which is resistant to chemical modification under mild conditions. In combination with high symmetry, this allows one to consider the octahedral cluster cores as a structural analogue of single metal ions, or "superatoms", which can act as the basis for creating building blocks with a specified geometry and properties by variation of the terminal ligand environment.…”

Section: ■ Introductionmentioning

confidence: 99%

Soluble Molecular Rhenium Cluster Complexes Exhibiting Multistage Terminal Ligands Reduction

et al. 2020

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Substitution of terminal halide ligands of octahedral rhenium cluster complexes [Re6Q8X6]4– in a melt of 4,4′-bipyridine (bpy) led to us obtaining four new compounds with the general formula trans-[Re6Q8(bpy)4X2] (Q = S or Se; X = Cl or Br) in high yield. In contrast to most of the known molecular rhenium cluster complexes with heteroaromatic terminal ligands, compounds 1–4 are soluble in organic solvents. This made it possible to carry out a detailed characterization of the new compounds both in solids and in solutions. In particular, it was shown that compounds 1–4 in the DMSO solution exhibit four reversible reduction processes. A comparison of the obtained data with the results of DFT calculations of the electronic structure suggests that these processes correspond to two-electron reduction of all four bpy ligands. The reduction potentials are shifted to the positive region compared with the potential of free bipyridine, and the value of the shift depends on the composition of the cluster core. The presence of four transitions also suggests that electronic exchange between terminal ligands in the cis-position is possible. The study of the luminescence of the compounds showed that emission maxima of selenide clusters almost coincide with those of sulfide ones, while luminescence spectra of the complexes with chloride terminal ligands (1 and 3) are slightly blue-shifted relative to the spectra of the complexes with bromide ligands (2 and 4).

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Section: ■ Introductionmentioning

confidence: 99%