Main content

1,2,3-Dithiazolyl and 1,2,3,5-Dithiadiazolyl Radicals as Spin-Bearing Ligands Towards the Design of New Molecular Materials

Show simple item record

dc.contributor.advisor Preuss, Kathryn
dc.contributor.author MacDonald, Daniel
dc.date.accessioned 2012-09-14T17:41:14Z
dc.date.available 2012-09-14T17:41:14Z
dc.date.copyright 2012-09
dc.date.created 2012-09-10
dc.date.issued 2012-09-14
dc.identifier.uri http://hdl.handle.net/10214/4000
dc.description.abstract A series of binuclear coordination complexes of 4-(2′-pyrimidal)-1,2,3,5-dithiadiazolyl and its selenium analogue have been prepared to examine their structural and magnetic properties. The zinc(II) coordination complex is the first example of a DTDA radical ligand N-coordinated to a diamagnetic metal center. The magnetic properties reveal that it exhibits Curie behaviour and can be used as a benchmark to compare the analogous coordination complexes which possess paramagnetic metal ions. The nickel(II) coordination complex of the selenium containing radical pymDSDA was shown to dimerize in the solid state and is the only binuclear complex thus far that has done so. The manganese(II) complex of pymDSDA is by far the most interesting and is isomorphous to the DTDA analogue. For both complexes, one of the two molecules in the asymmetric unit form chains in the solid state joined by intermolecular contacts between a sulfur or selenium atom from the radical, and an oxygen atom coordinated to a neighbouring molecule. This feature gives rise to a ground state spin greater than that of an individual binuclear coordination complex. The radical ligand is however disordered in the solid state and so these random chain lengths are dependent on the orientation of the ligands in adjacent complexes. The 1,2,3-DTA species examined herein are related to the 4,5-dioxo-4,5-dihydronaphtho[1,2-d][1,2,3]dithiazolyl radical and the related protonated species 4-hydroxy-5H-naphtho[1,2-d][1,2,3]dithiazol-5-one. The proton from this latter compound has shown that it can be substituted with alkyl groups and this was achieved using acetyl chloride to place an acetyl group in this position. The above radical did not exhibit the strong donor properties required for metal coordination and preliminary investigations of the radical dianionic suggest that it is chemically irreversible by cyclic voltametry. The acetyl group unfortunately did not provide the chemically reversibility of interest although has established a potential route toward the substitution chemistry of this compound. The other 1,2,3-DTA compounds discussed herein are not complete, although the data acquired on the precursor compounds leading up to the radical will be discussed. en_US
dc.language.iso en en_US
dc.rights.uri http://creativecommons.org/licenses/by/2.5/ca/ *
dc.subject Radical en_US
dc.subject coordination en_US
dc.subject complex en_US
dc.subject manganese en_US
dc.subject nickel en_US
dc.subject zinc en_US
dc.subject dithiadiazolyl en_US
dc.subject dithiazolyl en_US
dc.subject thiazyl en_US
dc.subject quinone en_US
dc.subject DTA en_US
dc.subject DTDA en_US
dc.subject magnet en_US
dc.subject magnetic en_US
dc.subject molecular en_US
dc.subject materials en_US
dc.subject science en_US
dc.subject nanotechnology en_US
dc.subject magnetism en_US
dc.title 1,2,3-Dithiazolyl and 1,2,3,5-Dithiadiazolyl Radicals as Spin-Bearing Ligands Towards the Design of New Molecular Materials en_US
dc.type Thesis en_US
dc.degree.programme Chemistry en_US
dc.degree.name Master of Science en_US
dc.degree.department Department of Chemistry en_US


Files in this item

Files Size Format View
MacDonald_Dan_201209_Msc.pdf 5.676Mb PDF View/Open

This item appears in the following Collection(s)

Show simple item record

http://creativecommons.org/licenses/by/2.5/ca/ Except where otherwise noted, this item's license is described as http://creativecommons.org/licenses/by/2.5/ca/