Electrochemical behaviors and relativistic DFT calculations to understand the terminal ligand influence on the [Re63-Q)8X6]4- clusters

Macarena Rojas-Poblete, Alexander Carreño, Manuel Gacitúa, Dayán Páez-Hernández, Walter A. Rabanal-León, Ramiro Arratia-Pérez

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

8 Citas (Scopus)

Resumen

A Born-Haber thermodynamic cycle was used to determine the redox potential in a series of rhenium(iii) clusters of the form [Re63-Q)8X6]4- where Q = S2- and Se2- and X = F-, Cl-, Br-, I-, CN-, NC-, SCN-, NCS-, OCN- and NCO-. Frequency analysis, relativistic and solvent effects were considered to estimate the free energy of the reversible process ReIII6/ReIII5ReIV at the DFT level. All the redox potentials were reported with respect to the standard hydrogen electrode (SHE) and show good agreement with the available experimental results. In general, the molecular orbitals involved in the redox process were localized in the cluster core, [Re63-Q)8]2+, and therefore the peripheral ligands act only as a modifier of the crystal-field strength, influencing the energy of the frontier molecular orbital splitting. Additionally, the theoretical approach was validated using an experimental protocol to study the electrochemical behavior of the [Re63-Se)8I6]3- cluster. An important first reversible reduction process was found at E1/2 = +0.47 V (SHE), which is in good agreement with the value predicted theoretically.

Idioma originalInglés
Páginas (desde-hasta)5471-5478
Número de páginas8
PublicaciónNew Journal of Chemistry
Volumen42
N.º7
DOI
EstadoPublicada - 1 ene 2018

Áreas temáticas de ASJC Scopus

  • Catálisis
  • Química (todo)
  • Química de los materiales

Huella

Profundice en los temas de investigación de 'Electrochemical behaviors and relativistic DFT calculations to understand the terminal ligand influence on the [Re<sub>6</sub>(μ<sub>3</sub>-Q)<sub>8</sub>X<sub>6</sub>]<sup>4-</sup> clusters'. En conjunto forman una huella única.

Citar esto