BEDT-TTF salts with square platinates(II) as counterions : [BEDT-TTF]4[Pt(C2O4)2], a new organic metal

Abstract

The title compound, [BEDT-TTF]4[Pt(C2O4)2] is obtained by electrocrystallization, which yields black platelets of stoichiometry C44H32O8PtS32, Mr = 1909.87. Crystal structure determination at room temperature gives a triclinic cell Pi, with a = 8.678(2) A, b =11.878(5) A, c = 15.757(7) A,α = 105.49(3)°, β= 91.05(3)", 'γ= 91.96(3)", V = 1563.64 A3,d c = 2.03 g/cm 3, Z = 1. The solid contains sheets of BEDT-TTF cations separated by sheets of [Pt(C2O4)2]2-- counterions. The BEDT-TTF sheets are made up of columns that interact strongly through S-S contacts. The columns are built up by pairs of BEDT-TTF molecules. There are strongly varying bond distances in the two different BEDT-TTF moieties that make up a pair. This fact is especially clearly expressed in the surprisingly short C-C distances of the central C=C double bond of the two BEDT-TTF ions:1.273 A and 1.327 A respectively. These are by far the shortest distances for the central C=C bonds observed so far in conductive BEDT-TTF salts. The compound behaves like a metal down to about 60 K. Temperature-dependent d.c. conductivity, e.s.r. and thermopower measurements show metallic behaviour at room temperature (σ300 = 20 S/cm) with a metal-to-metal phase transition around 200 K. At about 60 K a second broad phase transition occurs and the crystals become semiconducting.