Thiazyl radicals

J. M. Rawson and F. Palacio, Magnetic Properties of Thiazyl Radicals, Structure and Bonding, 100, 93 (2001). 

Christos Pantelis Constantinides is a Ph.D. student at the Department of Chemistry, The University of Cambridge, UK. He was born in Nicosia (1979) in Cyprus and obtained his Bachelor (2003) at the University of Cyprus, Nicosia. In 2005 Mr. Constantinides began his doctoral studies at the University of Cambridge working under the supervision of Dr. Jeremy Rawson and Dr. Stephen C. Moratti. His doctoral research focuses on the design, synthesis, and characterization of novel thiazyl radicals with magnetic and/or conducting properties. 

There has been considerable interest in the magnetic behaviour of thiazyl radicals because of the discovery of long-range magnetic order in derivatives of 2. 

Radicals have been known for many years to form organic paramagnetic materials with numerous magnetic properties (ferro- or ferri-magnetism, spin Peierls transition, spin frustration, spin ladder systems) (see [51-60] for verdazyl radicals, [61-68] for thiazyl radicals, [69] for nitronyl nitroxide and [70-78] for Tempo radicals) (Fig. 6). When they are in their cationic form, they are valuable candidates for an association with the M(dmit)2 systems they will then provide the magnetic properties thanks to their free electron(s), whereas the M(dmit)2 moieties will provide the electrical properties. 

Fig. 25. Schematic drawing of terphenyl-substituted thiazyl radicals and thioaminyls.121122 2. Phosphorus Compounds...

Heterocyclic thiazyl radicals hold considerable potential in the design of both conductive and magnetic materials. In the pursuit of improved conductivity, a series of resonance-stabilized radicals based on diselenadiazoles, sulfaselenazoles, and diselenazoles were obtained (185-188) (Fig. 17) [298-303], Structural analyses of 187 and 188 (R1 = Me, R2 = H) confirm that lattice and n-delocalization energies are sufficient to prevent solid state dimerization of the radicals. Incorporation of selenium leads to a dramatic increase in conductivity and reduction in thermal activation energy relative to sulfur-based radicals [300],... 

Preparation, crystal structures, and magnetic properties of 3-cyanobenzo-l,3,2-dithiazolyl radical were recently reported <2006IC1903>. The crystal structure and magnetic properties of thiazyl radicals and related materials have been reviewed <2006BCJ25>. 

Multidimensional crystal structures and unique solid-state properties of heterocyclic thiazyl radicals and related materials 06BCJ25. 

Figure 13 Thiazyl radicals demonstrating interesting magnetic and conducting properties.

---