| Summary: | A series of partially fluorinated 1,2,3,5-dithiadizolyl aryl derivatives was prepared, in order to examine the effects of the fluorinated substituents on the solid-state structure of these molecules. 3,5-(CF<sub>3</sub>)<sub>2</sub>(C<sub>6</sub>H<sub>3</sub>CNSSN and 3-CF<sub>3</sub>C<sub>6</sub>H<sub>4</sub>CNSSN were synthesized, as well as nine isomers of CF<sub>3</sub>FC<sub>6</sub>H<sub>3</sub>CNSSN. The crystal structures of seven of these derivatives are compared, and discussed in the light of their molecular electrostatic potential maps. 3-F-4-CF<sub>3</sub>C<sub>6</sub>H<sub>3</sub>CNSSN was found to crystallize as an inclusion compound with nitrogen. The synthesis and characterisation of this inclusion compound is described, as well as the reactivity of 3-F-4-CF<sub>3</sub>C<sub>6</sub>H<sub>3</sub>CNSSN to other small molecules (Ar, CO<sub>2</sub>, O<sub>2</sub>). Several fluorinated dithiadiazolyl derivatives were synthesized in order to investigate their physical properties. EPR studies on CF<sub>3</sub>CNSSN were undertaken in order to further examine its known bistable nature. EPR studies on the novel dithiadiazolyl derivative, CF<sub>3</sub>(CF<sub>2</sub>)<sub>6</sub>CNSSN are also described, and the possibility of this radical exhibiting a liquid crystalline phase is discussed. The synthesis and solid-state structure of novel monomeric dithiadiazolyl radical, (CF<sub>3</sub>)<sub>3</sub>C<sub>6 </sub>H<sub>2</sub>CNSSN, is also described. During the course of these studies, the known dithiadiazolyl derivative, CICNSSN, was synthesized in three concomitant polymorphic forms. The solid-state structure of these compounds is described, and the competing interactions seen in the three forms are discussed in the light of the molecular electrostatic potential map and atomic partial charges of CICNSSN. A series of novel dithiatetrazocines, <i>p</i>-X<sub>1</sub>C<sub>6</sub>H<sub>4</sub>C<sub>2</sub>N<sub>4</sub>S<sub>2</sub>C<sub>6 </sub>H<sub>4</sub>X<sub>2</sub> (X<sub>1</sub>, X<sub>2</sub> = NO<sub>2</sub>, Br) was synthesized and characterized in order to study the non-linear optical properties of the unsymmetric derivative. The solid-state structures of these three derivatives are described and rationalized using their molecular electrostatic potential maps.
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