Synthesis, Photochemical, and Redox Properties of Gold(I) and Gold(III) Pincer Complexes Incorporating a 2,2′:6′,2″-Terpyridine Ligand Framework

Gimeno, M. Concepción, López-de-Luzuriaga, José M., Manso, Elena, Monge, Miguel, Olmos, M. Elena, Rodríguez-Castillo, Mariá, Tena, María-Teresa, Day, David P., Lawrence, Elliot J. and Wildgoose, Gregory G. (2015) Synthesis, Photochemical, and Redox Properties of Gold(I) and Gold(III) Pincer Complexes Incorporating a 2,2′:6′,2″-Terpyridine Ligand Framework. Inorganic Chemistry, 54 (22). 10667–10677. ISSN 0020-1669

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    Abstract

    Reaction of [Au(C6F5)(tht)] (tht = tetrahydrothiophene) with 2,2′:6′,2″-terpyridine (terpy) leads to complex [Au(C6F5)(η1-terpy)] (1). The chemical oxidation of complex (1) with 2 equiv of [N(C6H4Br-4)3](PF6) or using electrosynthetic techniques affords the Au(III) complex [Au(C6F5)(η3-terpy)](PF6)2 (2). The X-ray diffraction study of complex 2 reveals that the terpyridine acts as tridentate chelate ligand, which leads to a slightly distorted square-planar geometry. Complex 1 displays fluorescence in the solid state at 77 K due to a metal (gold) to ligand (terpy) charge transfer transition, whereas complex 2 displays fluorescence in acetonitrile due to excimer or exciplex formation. Time-dependent density functional theory calculations match the experimental absorption spectra of the synthesized complexes. In order to further probe the frontier orbitals of both complexes and study their redox behavior, each compound was separately characterized using cyclic voltammetry. The bulk electrolysis of a solution of complex 1 was analyzed by spectroscopic methods confirming the electrochemical synthesis of complex 2.

    Item Type: Article
    Additional Information: This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
    Faculty \ School: Faculty of Science > School of Chemistry
    University of East Anglia > Faculty of Science > Research Groups > Physical and Analytical Chemistry
    University of East Anglia > Faculty of Science > Research Groups > Synthetic Chemistry
    Depositing User: Pure Connector
    Date Deposited: 03 Nov 2015 09:00
    Last Modified: 25 Jul 2018 11:15
    URI: https://ueaeprints.uea.ac.uk/id/eprint/54970
    DOI: 10.1021/acs.inorgchem.5b01477

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