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Separation of the ionic and electronic contributions to the overall thermodynamics of the insertion electrochemistry of some solid Au(I) complexes

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Abstract

Water-insoluble alkynyl-triphosphine tetranuclear Au(I) complexes containing ferrocenyl motifs, [Au4(C2R)2{(PPh2CH)2PPh}2](PF6)2 (L1, R = Fc; L2, R = C6H4Fc) produce, in contact with aqueous electrolytes, anion-assisted reversible solid-state oxidation/reduction reactions in voltammetry and a pure anion transfer reaction determining the open circuit potential in potentiometric measurements. The mid-peak potentials determined in voltammetry and the open circuit potential determined in potentiometry exhibit differences, which allow accessing the individual contributions of Gibbs energies of electron and ion transfer. This is the second example of a solid compound where this separation is possible. Monitoring of anion insertion by electron microscopy (field emission scanning microscopy/energy-dispersive X-ray analysis (FESEM/EDX)) experiments is reported.

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Acknowledgments

Special thanks go to Prof. Fritz Scholz for his valuable comments and discussion during the preparation of the manuscript. Financial support has been provided by the Spanish MYCINN CTQ2014-53736-C3-2-P project also supported by ERDF funds.

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Authors and Affiliations

  1. Departament de Química Analítica, Universitat de València, Dr. Moliner 50, 46100, Burjassot, Valencia, Spain

    Antonio Doménech-Carbó

  2. Department of Chemistry, University of Eastern Finland, 80101, Joensuu, Finland

    Igor O. Koshevoy

  3. Departament de Química Inorgànica, Universitat de València, Dr. Moliner 50, 46100, Burjassot, Valencia, Spain

    Noemí Montoya

Authors
  1. Antonio Doménech-Carbó
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  2. Igor O. Koshevoy
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  3. Noemí Montoya
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Correspondence to Antonio Doménech-Carbó.

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Doménech-Carbó, A., Koshevoy, I.O. & Montoya, N. Separation of the ionic and electronic contributions to the overall thermodynamics of the insertion electrochemistry of some solid Au(I) complexes. J Solid State Electrochem 20, 673–681 (2016). https://doi.org/10.1007/s10008-015-3092-4

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  • DOI: https://doi.org/10.1007/s10008-015-3092-4

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