Synthesis, Photochemical, and Redox Properties of Gold(I) and Gold(III) Pincer Complexes Incorporating a 2,2′:6′,2″-Terpyridine Ligand Framework
- Gimeno, M.C. 2
- López-De-Luzuriaga, J.M. 1
- Manso, E. 1
- Monge, M. 1
- Olmos, M.E. 1
- Rodríguez-Castillo, M. 1
- Tena, M.-T. 1
- Day, D.P. 3
- Lawrence, E.J. 3
- Wildgoose, G.G. 3
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1
Universidad de La Rioja
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2
Universidad de Zaragoza
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3
University of East Anglia
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ISSN: 0020-1669
Year of publication: 2015
Volume: 54
Issue: 22
Pages: 10667-10677
Type: Article
More publications in: Inorganic Chemistry
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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. © 2015 American Chemical Society.