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Keywords:

  • Molecular conductors;
  • ­Magnetic properties;
  • Sulfur heterocycles;
  • Rhenium;
  • Iron

Abstract

The synthesis, crystal structure and physical characterization of three radical salts of the donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) and tetrachloro(oxalato)rhenate(IV) {[ReCl4(C2O4)]2–} or tris(chloranilato)ferrate(III) {[Fe(C6O4Cl2)3]3–} anions are reported. The isolated salts with ReIV are (ET)[ReCl4(C2O4)] [1, monoclinic, space group C2/c with a = 18.3409(3) Å, b = 10.8414(2) Å, c = 11.1285(3) Å, β = 99.9714(7)°, V = 2179.38(8) Å3, Z = 4] and (ET)4[ReCl4(C2O4)]·C6H5CN [2, monoclinic, space group P21/c with a = 11.8549(2) Å, b = 32.9079(5) Å, c = 36.4154(5) Å, β = 96.742(2)°, V = 14108.1(4) Å3, Z = 8]. The salt with FeIII is (ET)6[Fe(C6O4Cl2)3]·(H2O)1.5·(CH2Cl2)0.5 [3, triclinic, space group Pequation image with a = 20.9489(7) Å, b = 26.7244(8) Å, c = 33.9132(11) Å, α = 68.262(3)°, β = 80.632(3)°, γ = 71.172(3)°, V = 16672.2(9) Å3, Z = 6]. Compounds 2 and 3 are two rare examples of paramagnetic molecular metals and the first ones in their respective families. Compound 3 has a very unusual θ21 phase and the largest number of independent ET molecules reported to date (18).