ChemInform Abstract: Ag_1+xTlO₂ (0.03 ≤ x ≤ 0.18), Novel Adaptations of the Delafossite Structure Type Featuring Subvalent Silver.

Abstract

Ag 1+xTlO2 (0.03  x  0.18), Novel Adaptations of the Delafossite Structure Type Featuring Subvalent Silver. -Phase-pure Ag 1+xTlO2 (x: 0.18 (I), 0.09 (II), 0.03 (III)) are prepared by reacting Ag 2O and TlNO3 or Tl2O3 in autoclaves (Au tube, 420 C, O2 pressure of 135 MPa for (I), 400 C, 200 h, 48 MPa for (II), and 200 C, 14 d for (III)). (I) crystallizes in the space group P3m1 (Z = 1) and (II) and (III) in the space group R3m (Z = 6 and 9, resp.) as determined by single crystal XRD. Different from the conventional delafossite structure, part of the Ag layers accommodate an excess of 0.18 Ag atoms per layer, thus generating a subvalent bonding state. In accordance with the structural findings, the new compounds are metallic conductors and show reduced binding energies for the Ag 3d 5/2 states compared to Ag2O. -(NUSS, J.; DIETRICH, V.; CURDA, J.; JANSEN*, M.; Z. Anorg. Allg. Chem. 640 (2014) 6, 1063-1068, http://dx.