Heterospin π-Heterocyclic Radical-Anion Salt: Synthesis, Structure, and Magnetic Properties of Decamethylchromocenium [1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl

Decamethylchromocene, Cr parallel to(eta(5)-C(5)(CH(3))(5))(2) (2), readily reduced [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) in a tetrahydrofuran solvent at ambient temperature with the formation of radical-anion salt [2](+)[1](-)- (3) isolated in 97% yield. The heterospin salt 3 ([2](+), S = (3)/2; [1](-), S = (1)/2) was characterized by single-crystal X-ray diffraction as well as magnetic susceptibility measurements in the temperature range 2-300 K. The experimental data together with theoretical analysis of the salt's magnetic structure within the CASSCF and spin-unrestricted broken-symmetry (BS) density functional theory (DFT) approaches revealed antiferromagnetic (AF) interactions in the crystalline 3: significant between anions [1](-), weak between cations [2r, and very weak between [1](-) and [2](+). Experimental temperature dependences of the magnetic susceptibility and the effective magnetic moment of 3 were very well reproduced in the assumption of the AF-coupled [1](-) ... [1](-) (J(1) = -40 +/- 9 cm(-1)) and [2](+) ... [2](+)-4- (J(2) = 0.58 +/- 0.03 cm(-1)) pairs. The experimental J1 value is in reasonable agreement with the value calculated using BS UB3LYP/ 6-31+G(d) (-61 cm(-1)) and CASSCF(10,10)/6-31+G(d) (-15.3 cm(-1)) approaches. The experimental J(2) value is also in agreement with that calculated using the BS DFT approach (-0.33 cm(-1)).