Date of Award
Chemistry and Biochemistry
Crystal Engineering, Magnetism, Metal Complexes, Radicals
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A series of p-XC6F4CNSSN radicals were prepared (X = Cl, Br) and polymorphs of each were discovered crystallographically. A comparison of the solid state structure of each was done to determine the supramolecular synthons dictating these new structures. Thermodynamic arguments have been proposed as to why these polymorphs form under the conditions they are isolated at. The magnetism of p-IC6F4CNSSN was also investigated and compared to its isomorphous radical, α-p-BrC6F4CNSSN. A new theory for forming ferrimagnetic materials is proposed. Radical co-crystals of TEMPO and RCNSSN radicals have been synthesized as a proof of concept and demonstrate the potential of this theory to yield organic magnetic materials. The cocrystal solid state structures were analyzed, and a qualitative hierarchy of supramolecular synthons was identified to illustrate the driving forces behind these structures. Metal complexes of the form Pd3(RCNSSN)2(PR3)4 have been synthesized. The effect of phosphine steric bulk and structural flexibility, alongside the electronic nature of the R group, is investigated.
Nascimento, Mitchell Anthony, "STRUCTURAL STUDIES AND CRYSTAL ENGINEERING OF DITHIADIAZOLYL RADICALS AND THEIR METAL COMPLEXES" (2018). Electronic Theses and Dissertations. 7458.