Synthesis and Characterization of Semiconductive Dichloridobis(thianthrene)gold(1+) Tetrachloridoaurate(1–)

A new (thianthrene)gold(III) complex has been synthesized in liquid SO 2 as the solvent from thianthrene (TA) andAuCl 3 . [AuCl 2 (TA) 2 ][AuCl 4 ] [triclinic, P $\bar {1}$ , a = 9.9832(2) Å, b = 10.3404(2) Å, c = 15.0798(4) Å, α = 75.038(1)°, β = 81.610(1)°, γ = 68.409(1)°, V = 1396.15(5) Å 3 , Z = 2] has a salt‐like structure consisting of [AuCl 2 (TA) 2 ] + and [AuCl 4 ] – ions, both with square‐planar coordinated gold atoms of oxidation state +3. In the cation, two bent TA molecules are coordinated to Au each through one sulfur atom. The title compound is thermally stable up to 425 K and is semiconducting with a conductivity reaching 25 mSm –1 at 380 K and a low activation energy of 0.43 eV. A model for the charge transport along the stacked cationic complexes is discussed. When dissolved in chloroform [AuCl 2 (TA) 2 ][AuCl 4 ] is converted into the already known uncharged, mononuclear complex [AuCl 3 (TA)], which shows that a polymerization isomerism exists between the two forms.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)