title: Structural, electrochemical and spectroelectrochemical study on the geometric and electronic structures of [(corrolato)Au(III)](n) (n = 0, +1, -1) complexes.
abstract: Synthesis of two new Au(III) corrole complexes with unsymmetrically substituted corrole ligands is presented here. The newly synthesized Au-compounds have been characterized by various spectroscopic techniques. The structural characterization of a representative Au(III) corrole has also been possible. Electrochemical, UV-vis-NIR/EPR spectroelectrochemical and DFT studies have been used to decipher the electronic structures of various electro-generated species. These are the first UV-vis-NIR/EPR spectroelectrochemical investigations on Au(III) corroles. Assignment of redox states of electro-generated Au(III) corroles is supported by DFT analysis. In contrast to the metal centered reduction reported in Au(III) porphyrins, one electron reduction in Au(III) corroles has been assigned to corrole centered on the basis of experimental and theoretical studies. Thus, the Au(III) corroles (not the analogous Au(III) porphyrin derivatives!) bear a truly redox inactive Au(III) center. Additionally, these Au-corrole complexes display NIR electrochromism, the origin of which is all on corrole-centered processes.
authors.affiliation: School of Chemical Sciences, National Institute of Science Education and Research (NISER), Bhubaneswar - 751005, India. sanjib@niser.ac.in.
authors.forename: Woormileela
authors.initials: W
authors.lastname: Sinha
authors.forename: Michael G
authors.initials: MG
authors.lastname: Sommer
authors.forename: Margarethe
authors.initials: M
authors.lastname: van der Meer
authors.forename: Sebastian
authors.initials: S
authors.lastname: Plebst
authors.forename: Biprajit
authors.initials: B
authors.lastname: Sarkar
authors.forename: Sanjib
authors.initials: S
authors.lastname: Kar