Unique Superparamagnetic-like Behavior Observed in Non-π-delocalized Nitroxide Diradical Compounds Showing Discotic Liquid Crystalline Phase

A unique superparamagnetic-like behavior and a large “positive magneto-LC effect” were observed in the solid phases and the hexagonal columnar (Col_h) liquid crystalline (LC) phase, respectively, of novel achiral non-π-delocalized nitroxide diradical compounds (R,S)-1, which showed polymorphism in the solid phases (solids I and II). The SQUID magnetization measurement revealed that (1) (R,S)-1 containing a small amount of racemic diastereomers (R*,R*)-1 possessed an unusual and large temperature-independent magnetic susceptibility (χ_TIM>0) component in the original nanocrystalline solid I that was responsible for the observed superparamagnetic-like behavior under low magnetic fields and did not arise from the contamination by extrinsic magnetic metal or metal ion impurities, besides ordinary temperature-dependent paramagnetic susceptibility (χ_para>0) and temperature-independent diamagnetic susceptibility (χ_dia<0) components, (2) a large increase in molar magnetic susceptibility (χ_M) (positive magneto-LC effect) that occurred at the solid I-to-liquid crystal transition upon heating was preserved as an additional χ_TIM increase in the resulting polymorphic nanocrystalline solid II by cooling, and (3) such unique magnetic phenomena were induced by thermal processing for (R,S)-1 or by adding a small amount of (R*,R*)-1 to (R,S)-1 as the impurity.