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

摘要

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) {[ReCl_4(C_2O_4)]~(2-)} or tris(chloranilato)ferrate(III) {[Fe(C_6O_4Cl_2)_3]~(3-)} anions are reported. The isolated salts with ReIV are (ET)[ReCl_4(C_2O_4)] [1, monoclinic, space group C2/c with a = 18.3409(3) ?, b = 10.8414(2) ?, c = 11.1285(3) ?, β = 99.9714(7)°, V = 2179.38(8) ?~3, Z = 4] and (ET)_(4~-) [ReCl_4(C_2O_4)]·C_6H_5CN [2, monoclinic, space group P2_1/c with a = 11.8549(2) ?, b = 32.9079(5) ?, c = 36.4154(5) ?, β = 96.742(2)°, V = 14108.1(4) ?3, Z = 8]. The salt with Fe~(III) is (ET)_6[Fe(C_6O_4Cl_2)_3]·(H_2O)_(1.5)·(CH_2Cl_2)_(0.5) [3, triclinic, space group P1 with a = 20.9489(7) ?, b = 26.7244(8) ?, c = 33.9132(11) ?, α = 68.262(3)°, β = 80.632(3)°, γ = 71.172(3)°, V = 16672.2(9) ?~3, 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 θ~(21) phase and the largest number of independent ET molecules reported to date (18).