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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

AutorGimeno, 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.
Fecha de publicación2015
EditorAmerican Chemical Society
CitaciónInorganic Chemistry 54(22): 10667-10677 (2015)
ResumenReaction 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.
Versión del editorhttps://doi.org/10.1021/acs.inorgchem.5b01477
URIhttp://hdl.handle.net/10261/154731
DOI10.1021/acs.inorgchem.5b01477
Identificadoresdoi: 10.1021/acs.inorgchem.5b01477
e-issn: 1520-510X
issn: 0020-1669
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