Gold(III) Complexes of Asymmetrically Aryl-Substituted 1,2-Dithiolene Ligands Featuring Potential-Controlled Spectroscopic Properties: An Insight into the Electronic Properties of bis(Pyren-1-yl-ethylene-1,2-dithiolato)Gold(III)

摘要

The electrochemical, UV/ Vis-NIR absorption, and emission-spectroscopic features of (TBA~(+))(1~(-)) and the corresponding neutral complex 1 were investigated (TBA~(+)(velence)tetrabutylammonium; 1~(-) velence [Au~(III)(Pyr,H-edt)_(2)]~(-); Pyr,H-edt~(2-) velence pyren-1-yl-ethylene-1,2-dithiolato). The intense electrochromic NIR absorption ((lambda)_(max)velence1432 nm; epsilon velence 13000M~(-1) cm~(-1) in CH_(2)Cl_(2)) and the potential-controlled visible emission in the range 400-500 nm, the energy of which depends on the charge of the complex, were interpreted on the grounds of time-dependent DFT calculations carried out on the cis and trans isomers of 1, 1~(-), and 1~(2-). In addition, to evaluate the nonlinear optical properties of 1~(x-) (x(velence)0, 1), first static hyperpolarizability values (beta)_(tot) were calculated ((beta)_(tot)velence78 X 10~(-30) and 212 X 10~(-30) esu for the cis isomer of 1~(-) and 1, respectively) and compared to those of differently substituted [Au(Ar,H-edt)_(2)]~(x-) gold dithiolenes [Ar(velence)naphth-2-yl (2), phenyl (3); x(velence)0, 1].