Bistabilities in 1,3,2-Dithiazolyl Radicals

New synthetic methods for heterocyclic 1,3,2-dithiazolyl (DTA) radicals have been developed, and trends in the molecular spin distributions and electrochemical properties of a series of DTA radicals are reported. The crystal structures of [1,2,5]thiadiazolo[3,4-f][1,3,2]benzodithiazol-2-yl (TBDTA) and [1,3,2]pyrazinodithiazol-2-yl (PDTA) have been determined. The structure of TBDTA (at 293 and 95 K) contains two molecules in the asymmetric unit, each of which generates pi-stacked arrays, one consisting of antiparallel chains of centrosymmetrically associated dimers, the other comprising parallel chains of unassociated radicals. The structure of PDTA (at 293 and 95 K) is simpler, consisting of slipped stacks of pi-dimers. Variable-temperature magnetic susceptibility (chi(P)) measurements on TBDTA indicate essentially paramagnetic behavior for the unassociated radical pi-stacks over the range 5-400 K. By contrast PDTA is diamagnetic at all temperatures below 300 K, but between 300 and 350 K the value of chi(P) follows a sharp and well-defined hysteresis loop, with T(C) downward arrow = 297 K and T(C) upward arrow = 343 K. These features are symptomatic of a regime of bistability involving the observed low temperature pi-dimer structure and a putative high-temperature radical pi-stack. A mechanism for the interconversion of the two phases of PDTA and related structures is proposed in which hysteretic behavior arises from cooperative effects associated with the breaking and making of a lattice-wide network of intermolecular S- - -N' and/or S- - -S' interactions.