A series of diradical containing salts CxF2x(CNSSS)(2)(center dot center dot 2+)(AsF6-)2 {X = 2, 1[AsF6](2); x = 3, 3[AsF6](2); x = 4, 2[AsF6](2)} have been prepared. 1[AsF6](2) and 2[AsF6](2) were fully characterized by X-ray, variable-temperature magnetic susceptibility, and solid-state EPR measurements, further allowing us to extend the number of examples of the family of rare 7 pi RCNSSS center dot+ radical cations. 1[AsF6](2): a = 6.5314(7) angstrom, b = 7.5658(9) angstrom, c = 9.6048(11) angstrom, alpha = 100.962(2)degrees, = 96.885(2)degrees, gamma = 107.436(2)degrees, triclinic, space group P (1) over bar, Z = 1, T = 173 K. 2[AsF6](2): a = 10.6398(16) angstrom, b = 7.9680(11) angstrom, c = 12.7468(19) angstrom, beta = 99.758(2)degrees, monoclinic, space group P2(1)/c, Z = 2, T = 173 K. In the solid-state, CxF2x(CNSSS)(2)(center dot center dot 2+) (x = 2, 4) formed one-dimensional polymeric chains of dications containing discrete centrosymmetric radical pairs in which radicals were linked by four centered two-electron pi*- pi* bonds [1(2+), d(S center dot center dot center dot S) = 3.455(1) angstrom; 2(2+), d(S center dot center dot center dot S) = 3.306(2) angstrom]. The exchange interactions in these bonds were determined to be -500 +/- 30 and -900 +/- 90 cm(-1), by variable temperature magnetic susceptibility measurements, respectively, providing rare experimental data on the singlet-triplet gaps in the field of thiazyl radicals. For 2[AsF6](2), the thermally excited triplet state was unambiguously characterized by EPR techniques [vertical bar D vertical bar = 0.0254(8) cm(-1), vertical bar E vertical bar = 0.0013(8) cm(-1)]. These experimental data implied a weakly associated nature of the radical moieties contained in the solids 1[AsF6](2) and 2[AsF6](2). Computational analysis of the dimerization process is presented, and we show that the 2c 4 electron pi*-pi* bonds in 1[AsF6](2) and 2[AsF6](2) have ca. 50% and 40% diradical character, respectively. In contrast, 3[AsF6](2)center dot SO2, containing diradical C3F6(CNSSS)(2)(center dot center dot 2+) with an odd number of CF2 spacers, showed magnetic behavior that was consistent with the presence of monomeric radical centers in the solid state.