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Synthesis, photochemical, and redox properties of gold(I) and gold(III) pincer complexes incorporating a 2,2′:6′,2″- terpyridine ligand framework

AuthorsGimeno, M. Concepción ; López-de-Luzuriaga, José M.; Manso, Elena; Monge, Miguel; Olmos, M. Elena; Rodríguez-Castillo, María; Tena, María-Teresa; Day, David P.; Lawrence, Elliot J.; Wildgoose, Gregory G.
Issue Date2015
PublisherAmerican Chemical Society
CitationInorganic Chemistry 54(22): 10667-10677 (2015)
AbstractReaction of [Au(CF)(tht)] (tht = tetrahydrothiophene) with 2,2′:6′,2″-terpyridine (terpy) leads to complex [Au(CF)(η-terpy)] (1). The chemical oxidation of complex (1) with 2 equiv of [N(CHBr-4)](PF) or using electrosynthetic techniques affords the Au(III) complex [Au(CF)(η-terpy)](PF) (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.
Publisher version (URL)https://doi.org/10.1021/acs.inorgchem.5b01477
Identifiersdoi: 10.1021/acs.inorgchem.5b01477
e-issn: 1520-510X
issn: 0020-1669
Appears in Collections:(ISQCH) Artículos
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