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Issue 7, 2018
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Electrochemical behaviors and relativistic DFT calculations to understand the terminal ligand influence on the [Re63-Q)8X6]4− clusters

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Abstract

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.

Graphical abstract: Electrochemical behaviors and relativistic DFT calculations to understand the terminal ligand influence on the [Re6(μ3-Q)8X6]4− clusters

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Publication details

The article was received on 24 Dec 2017, accepted on 19 Feb 2018 and first published on 26 Feb 2018


Article type: Paper
DOI: 10.1039/C7NJ05114J
Citation: New J. Chem., 2018,42, 5471-5478
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    Electrochemical behaviors and relativistic DFT calculations to understand the terminal ligand influence on the [Re63-Q)8X6]4− clusters

    M. Rojas-Poblete, A. Carreño, M. Gacitúa, D. Páez-Hernández, W. A. Rabanal-León and R. Arratia-Pérez, New J. Chem., 2018, 42, 5471
    DOI: 10.1039/C7NJ05114J

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