Novel organic magnetic conductors based on organochalcogen donors and an organic magnetic anion, TEMPO-NHCOCH2SO3−

We report here four novel purely organic magnetic conductors containing common electron donors together with an organic anion including an organic free radical, (TTF)(TEMPO-NHCOCH2SO3)·0.5H2O (1), (TMTSF)(TEMPO-NHCOCH2SO3)·2H2O (2), (BEDT-TTF)3(TEMPO-NHCOCH2SO3)2·2H2O (3), and α-(BEDT-TTF)3(TEMPO-NHCOCH2SO3)2·6H2O (4). The TTF complex was prepared by metathesis of (TTF)3(BF4)2 and the PPh4 salt of the anion (5). The other complexes were obtained by electrocrystallization of the corresponding donors with the salt 5 as an electrolyte. Crystal structures of 2-4 have been solved. The salts 1 and 2 show relatively high resistivities (>107 and 5 × 103 Ω·cm), whilst the BEDT-TTF salts 3 and 4 have rather low room temperature resistivities (1.2 and 5.1 Ω·cm) with small activation energies (0.041 and 0.050 eV). The magnetic behavior of complex 1 obeys the Curie-Weiss law (C = 0.379 emu·K/mol and θ = −3.29 K) and those of the other complexes obey the 1-D Heisenberg model (C/J = 0.366/−0.32 for 2, 0.373/−0.81 for 3, and 0.380 emu·K·mol−1/+0.42 K for 4). The relationships between the crystal structures and the physical properties are discussed.