Metallic Charge‐Transfer Salts of Bis(ethylenedithio)tetrathiafulvalene with Paramagnetic Tetrachloro(oxalato)rhenate(IV) and Tris(chloranilato)ferrate(III) Anions

Abstract

AbstractThe 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 P$\bar {1}$ 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).