Electronic and Magnetic Interactions in π-Stacked Bisthiadiazinyl Radicals

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 π-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 σ(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 π-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 π-stacks is weak and the material is essentially paramagnetic. When R1
= Et, intermolecular π-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.