The preparation of two bisthiadiazinyls (7, R1 = Me, Et; R2 = Cl, R3 = Ph), the first examples of a new class of resonance-stabilized heterocyclic thiazyl radical, are reported. Both radicals have been characterized in solution by EPR spectroscopy and cyclic voltammetry, which confirm highly delocalized spin distributions and low electrochemical cell potentials, features which augur well for the use of these materials as building blocks for neutral radical conductors. In the solid state, the radicals are undimerized, crystallizing in slipped pi-stack arrays which ensure the availability of electrons as potential charge carriers. However, despite these favorable electrochemical and structural properties, both materials exhibit low conductivities, with sigma(300K) < 10-7 S cm-1, a result which can be rationalized in terms of their EHT band electronic structures, which indicate that intermolecular interactions lateral to the pi-stacks are limited. The materials are thus very 1-D with low bandwidths, so that a Mott insulating state prevails. When R1 = Me, the intermolecular overlap along the pi-stacks is weak and the material is essentially paramagnetic. When R1 = Et, intermolecular pi-overlap is greater and variable-temperature magnetic susceptibility measurements indicate a strongly antiferromagnetically coupled system, the behavior of which has been modeled in terms of a molecular-field modified 1-D Heisenberg chain of S = 1/2 centers. Broken-symmetry DFT methods have been used to estimate the magnitude of individual exchange interactions within both structures.