Toward a more general synthetic route to paramagnetic solids containing RCNSSS center dot+ radical cations. A structure-property correlation for RCNSSS center dot+ (R = F5C2, Cl3C)

Decken A; Mattar SM; Passmore J; Shuvaev KV; Thompson LK

Inorganic Chemistry, Vol.45, No.10, 3878-3886, 2006

Decken A, Mattar SM, Passmore J, Shuvaev KV, Thompson LK

Reaction of Cl3CN and F5C2CN with a 1:1 mixture of S-4(AsF6)(2) and S-8(AsF6)(2) affords the paramagnetic solids Cl3CNSSSAsF6 (1CCl(3)AsF(6)) and F5C2CNSSSAsF6 (1C(2)F(5)AsF(6)). Isotropic electron paramagnetic resonance spectra of 1CCl(3)AsF(6) and 1C(2)F(5)AsF(6) in SO2 consist of a single line with g = 2.01675 and 2.01580, respectively. The structure of 1CCl(3)AsF(6) contains chains of radical cations with relatively close interchain interactions. In contrast, chains are isolated in 1C(2)F(5)AsF(6). The magnetic behavior of both compounds was interpreted as that of 1D Heisenberg antiferromagnetic chains (1CCl(3)AsF(6), J = -34 cm(-1), theta = -9 cm(-1), TIP = 0.00082, rho = 0.012; 1C(2)F(5)AsF(6), J = -21 cm(-1), theta = -4.2 cm(-1), TIP = 0.00092, rho = 0.065). Density functional theory calculated and experimental magnetic coupling constants were in good agreement. The correlation between intermolecular S center dot center dot center dot S contacts and the strength of magnetic couplings was established.