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

• Main Author: Baddour, Frederick G.
• Language: en_US
• Published: 2016
• Subjects: Chemistry; Heterobimetallics; One-dimensional
• Online Access: https://hdl.handle.net/2144/17746

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.