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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Platinum-containing heterobimetallic lantern complexes prepared with thiocarboxylates: synthesis, structural, and magnetic characterization and synthesis characterization of magnetic metal oxide nanoparticles

Baddour, Frederick G. 12 August 2016 (has links)
Three Pt-based heterobimetallic lantern complexes of the form, [PtM(SAc)4(OH2)], M = Co (1), Ni (2), Zn (3), were prepared with thioacetate (SAc^-) bridging ligands that exhibit short Pt^...Pt interactions in the solid state. Three compounds with the form [PtM(SAc)4(3-NO2py)], M = Co (4), Ni (5), Zn (6) are formed upon reaction with 3-nitropyridine (3-NO2py) or alternatively the hydrated species 1--3 could be dehydrated to form the species [PtM(SAc)4], M = Co (7), Ni (8), Zn (9). Solid-state magnetism measurements indicate antiferromagnetic coupling of the paramagnetic 3d metal centers that can be attributed to the pathway established by the short Pt^...Pt contacts. Additional families of thiocarboxylate lantern complexes were prepared via the reaction of 1--3 or 7--9 with nitrogen or oxygen donor ligands. Reaction of 7--9 with pyridine yielded complexes with the form [PtM(SAc)4(py)2], M = Co (10), Ni (11), Zn (12). Complexes 10--12 could be thermally converted to the complexes [PtM(SAc)4(py)], M = Co (13), Ni (14), Zn (15) respectively. Reactions with the 4-aminopyridine ligand (amp) yielded exclusively monopyridyl species of the form [PtM(SAc)4(amp)], M = Co (16), Ni (17), Zn (18). O-donor solvents bind the dehydrated core [PtM(SAc)4] to give the complexes [PtCo(SAc)4(DMSO)](DMSO), 19, and [PtNi(SAc)4(DMF)](DMF), 20. Several diamagnetic complexes were prepared with the form [PtM(SOCR)4OH2], R = CH3, M = Mg (21); R = C6H5, M = Mg (22), Ca (23), and Zn (24) to examine the effect of the 3d metal on the electronic environment as determined by ^195Pt NMR. An additional family of complexes were prepared with pyrazine (pyz) linker ligands to form coordination polymers of the form [PtM(SAc)4(pyz)]n M = Co (25), Ni (26), Zn (27) and [PtM(SAc)4(pyz)0.5]2 M = Co (28), Ni (29), Zn (30). Two novel diplatinum complexes have been prepared with the 2,6-dimercaptopyridine (H2dmp) protoligand of the form [Pt2(Hdmp)4], 31, and [Pt2(phen)2(Hdmp)2], 32. Finally, a facile synthesis for ricinoleic acid, RA, coated ferrite spinel nanoparticles MFe2O4 · RA, M = Mn (33), Co (34), Ni(35), Zn(36) has been developed. The ferrite spinels were prepared hydrothermally and the synthesis and characterization of these nanoparticles will be discussed.

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