Reduction of [([Formula: see text])2][As6]2 with triphenylantimony and tetrabutylammonium chloride produced the diradical 5,5'-bis(1,3,2,4-dithiadiazolyl) [[Formula: see text]-[Formula: see text]] in high yield as a black solid with widely ranging magnetic susceptibilities (e.g., 0.6 to 2.6 μB), which on oxidation with AsF5 regenerated [([Formula: see text])2][AsF6]2. The identity of [[Formula: see text]-[Formula: see text]] was established from EPR, vibrational, and mass spectra. Ab initio molecular orbital [MPW1PW91/6-311G(2df)] calculations show the lowest energy structure to consist of two coplanar rings separated by a CC single bond (1.444 Å), reflected in the comparison of the vibrational spectra of the diradical with that of [([Formula: see text])2][AsF6]2 and the calculated spectra. Confidence in the calculated [MPW1PW91/6-311G(2df)] structure of the diradical is supported by the excellent agreement between the calculated and X-ray single crystal structure geometries of [[Formula: see text]]2 and [([Formula: see text])2]2+ in [([Formula: see text])2][AsF6]2. The molecular orbitals indicate the diradical is essentially disjoint, confirmed by a very small (0.07 kJ mol1) GVB-PP(TC-SCF)/6-311G* calculated singlettriplet energy gap. Accordingly, the EPR spectrum of the diradical (in tetrahydrofuran, 293 K) shows a simple 3-line pattern (g = 2.0043, a(14N) = 1.11 mT) with no observable exchange coupling between the two radical centers. Mechanical grinding of the diradical results in a large increase in paramagnetism (e.g., from 1.03 to 2.55 μB) that is unprecedented in main group chemistry. The X-ray diffraction data of the ground and unground powder are consistent with a second order phase change on grinding. Attempts to obtain crystals of the diradical by sublimation led instead to numerous decomposition and rearrangement products, including 4-cyano-1,2,3,5-dithiadiazolyl [NC-[Formula: see text]], monoclinic space group C2/c, a = 9.46(2) Å, b = 7.625(5) Å, c = 13.17(2) Å, β = 107.94(4)°, Z = 8. The structure consists of axially symmetric, co-facial, cis dimers linked to form strands through two sets of C[Formula: see text]Nδ···Sδ+ contacts. More efficient and larger scale preparations of [SNS][AsF6] and [([Formula: see text])2][AsF6]2 are reported. Key words: 5,5'-bis(1,3,2,4-dithiadiazolyl), diradical, paramagnetism, mechanical grinding, second order phase change, 4-cyano-1,2,3,5-dithiadiazolyl.