RESUMO
The neutral radical 4-(2'-benzimidazolyl)-1,2,3,5-dithiadiazolyl (HbimDTDA) exhibits a first order phase transition around 270 K without symmetry breaking, preserving its orthorhombic Pbca space group between 340 and 100 K. Associated with this reversible single-crystal-to-single-crystal phase transition, thermal hysteresis of the magnetic susceptibility is observed. The low temperature (LT) phase is diamagnetic owing to pancake bonding between the π-radicals. In the paramagnetic high temperature (HT) phase, the pancake bonds are broken, and new electrostatic contacts are apparent. As a result of the dense 3D network of supramolecular contacts, which includes H-bonds, the HbimDTDA system provides the first example of magnetic bistability for a DTDA radical.
RESUMO
A versatile synthetic methodology to access the first family of chiral verdazyl N,N'-chelate ligands is described and exemplified by N,N'-dimethyl-, N,N'-di-isopropyl- and N,N'-diphenyl oxoverdazyls bearing two isomers of the pinene-pyridine functional group. Their physical properties were probed by X-band EPR spectroscopy, cyclic voltammetry and DFT calculations. Preliminary reactivity studies show they can act as N,N'-chelate ligands affording a chiral 1 : 1 complex (3b) with CuCl2, which was characterized by single-crystal X-ray diffraction. Variable temperature EPR studies on (3b) confirm the presence of antiferromagnetic interactions between the spins of the Cu(ii) ion and the verdazyl radical.