Synthesis, Photochemical, and Redox Properties of Gold(I) and Gold(III) Pincer Complexes Incorporating a 2,2鈥?6鈥?2鈥?Terpyridine Ligand Framework

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• 作者：M. Concepci贸n Gimeno ; Jos茅 M. L贸pez-de-Luzuriaga ; Elena Manso ; Miguel Monge ; M. Elena Olmos ; Mar铆a Rodr铆guez-Castillo ; Mar铆a-Teresa Tena ; David P. Day ; Elliot J. Lawrence ; Gregory G. Wildgoose
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：November 16, 2015
• 年：2015
• 卷：54
• 期：22
• 页码：10667-10677
• 全文大小：475K
• ISSN：1520-510X

文摘

Reaction of [Au(C<sub>6sub>F<sub>5sub>)(tht)] (tht = tetrahydrothiophene) with 2,2鈥?6鈥?2鈥?terpyridine (terpy) leads to complex [Au(C<sub>6sub>F<sub>5sub>)(畏<sup>1sup>-terpy)] (1). The chemical oxidation of complex (1) with 2 equiv of [N(C<sub>6sub>H<sub>4sub>Br-4)<sub>3sub>](PF<sub>6sub>) or using electrosynthetic techniques affords the Au(III) complex [Au(C<sub>6sub>F<sub>5sub>)(畏<sup>3sup>-terpy)](PF<sub>6sub>)<sub>2sub> (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.