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Titolo: Synthesis and Characterization of Novel Gold(III) Complexes of Asymmetrically Aryl-Substituted 1,2-Dithiolene Ligands Featuring Potential-Controlled Spectroscopic Properties
Data di pubblicazione: 2010
Abstract: The tetrabutylammonium (TBA+) salts of square-planar monoanionic gold complexes of the unsymmetrically substituted Ar,H-edt2− 1,2-dithiolene ligands (Ar,H-edt2−=arylethylene-1,2-dithiolato; Ar=phenyl (1−), 2-naphthyl (2−), and 1-pyrenyl (3−)) were synthesized and characterized by spectroscopic and electrochemical methods and the corresponding neutral species (1, 2, and 3, respectively) were obtained in CH2Cl2 solution at room temperature by diiodine oxidation. The single-crystal X-ray diffraction structural data collected for (TBA+)(2−), supported by DFT theoretical calculations, are consistent with the ene-1,2-dithiolate form of the ligand and the AuIII oxidation state. All complexes feature intense near-IR absorptions (at about 1.5 μm) in their neutral states and Vis-emitting properties in the 400–550 nm range, the energy of which is controlled by the charge of the complex in the case of the 3−/3 couple. The spectroscopic and electrochemical features of 1x− and 2x− (x=0, 1), both in their cis and trans conformations, were investigated by means of DFT and time-dependent (TD) DFT calculations.
Tipologia:1.1 Articolo in rivista

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