Electrochemically generated peryleniumyl-hexafluorophosphate and hexafluoroarsenate : new one-dimensional metals

Abstract

Compounds of stoichiometry (pe)2(PF6)1.1x times 0.8CH2Cl2(1) (pe = perylene), (pe)2(AsF6)1.1 timesx 0.7 CH2Cl2 (2), (pe)2(PF6)1.4 times 0.6 THF (3), (pe)2(AsF6)1.5x times 0.5 THF (4) and (pe)3(SbF6)2 times 0.75 CH2Cl2 (5) have been obtained as crystalline samples by electrochemical deposition from CH2Cl2 [(1), (2) and (5)] or from THF [(3) and (4)] solutions of perylene, containing the appropriate counterion. The three compounds (1)-(3) crystallize in isomorphous orthorhombic lattices. (1) forms black needles: space group Pnmn with a = 4.285 Aring, b = 12.915 Aring and c = 14.033 Aring, z = 1. (2) gives black needles, orthorhombic space group Pnmn with a = 4.294 Aring, b = 13.077 Aring, and c = 14.132 Aring, z = 1. The structures of (1) and (2) were solved by direct methods and refined by least squares to final R = 0.148 and R = 0.088 based on 476 and 322 observed reflections. The perylene forms segregated stacks in direction of the a-axis with interplanar distances of 3.40 Aring and an angle of 37.7° between the bc-plane and the perylene. The channels between the segregated stacks are filled by anions and solvent molecules. The d.c. conductivities (four probe measurements) of (1)-(4) fall in the range of 70-1200Ω-1. cm-1 at room temperature. The conductivities show a metallic regime down to about 200°K and drop off below that temperature.