Synthesis, Photochemical, and Redox Properties of Gold(I) and Gold(III) Pincer Complexes Incorporating a 2,2':6',2"-Terpyridine Ligand Framework.
Reaction of [Au(C6F5)(tht)] (tht = tetrahydrothiophene) with 2,2':6',2"-terpyridine (terpy) leads to complex [Au(C6F5)(η(1)-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)(η(3)-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.
Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Universidad de Zaragoza-CSIC , 50009-Zaragoza, Spain.
M Concepción
MC
Gimeno
Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico Tecnológico, 26004-Logroño, Spain.
José M
JM
López-de-Luzuriaga
Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico Tecnológico, 26004-Logroño, Spain.
Elena
E
Manso
Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico Tecnológico, 26004-Logroño, Spain.
Miguel
M
Monge
Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico Tecnológico, 26004-Logroño, Spain.
M Elena
ME
Olmos
Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico Tecnológico, 26004-Logroño, Spain.
María
M
Rodríguez-Castillo
Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico Tecnológico, 26004-Logroño, Spain.
María-Teresa
MT
Tena
School of Chemistry, University of East Anglia , Norwich Research Park, Norwich NR47TJ, United Kingdom.
David P
DP
Day
School of Chemistry, University of East Anglia , Norwich Research Park, Norwich NR47TJ, United Kingdom.
Elliot J
EJ
Lawrence
School of Chemistry, University of East Anglia , Norwich Research Park, Norwich NR47TJ, United Kingdom.
Gregory G
GG
Wildgoose