Studies on a “Disappearing Polymorph”: Thermal and Magnetic Characterization of α‑p‑NCC6F4CNSSN•

The α-and β-phases of the thiazyl radical p-NCC6F4­CNSSN• (1) can be selectively prepared by careful control of the sublimation conditions, with the α-phase crystallizing preferentially when the substrate temperature is maintained below −10 °C, whereas the β-phase is isolated when the substrate temperature is maintained at or above ambient temperature. Differential scanning calorimatry studies reveal that the α-phase converts to the β-phase upon warming over the range 111–117 °C (ΔH = +4 kJ·mol–1) via a melt–recrystallization process, with the β-phase itself melting at 167–170 °C (ΔHfus = 27 kJ·mol–1). IR and Raman spectroscopy can be used to clearly discriminate between 1α and 1β. The α-phase shows a broad maximum in the magnetic susceptibility around 8 K that, coupled with a broad maximum in the heat capacity, is indicative of short-range order. Some field dependence of the susceptibility below 3 K is observed, but the lack of features in the ac susceptibility, M vs H plots, or heat capacity mitigates against long-range order in 1α.