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

  1. Gimeno, M.C. 2
  2. López-De-Luzuriaga, J.M. 1
  3. Manso, E. 1
  4. Monge, M. 1
  5. Olmos, M.E. 1
  6. Rodríguez-Castillo, M. 1
  7. Tena, M.-T. 1
  8. Day, D.P. 3
  9. Lawrence, E.J. 3
  10. Wildgoose, G.G. 3
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Universidad de Zaragoza
    info

    Universidad de Zaragoza

    Zaragoza, España

    ROR https://ror.org/012a91z28

  3. 3 University of East Anglia
    info

    University of East Anglia

    Norwich, Reino Unido

    ROR https://ror.org/026k5mg93

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Revista:
Inorganic Chemistry

ISSN: 0020-1669

Año de publicación: 2015

Volumen: 54

Número: 22

Páginas: 10667-10677

Tipo: Artículo

DOI: 10.1021/ACS.INORGCHEM.5B01477 SCOPUS: 2-s2.0-84947562642 WoS: WOS:000364981300021 GOOGLE SCHOLAR

Otras publicaciones en: Inorganic Chemistry

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Resumen

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. © 2015 American Chemical Society.