| This thesis describes the design, synthesis and characterization of platinum containing supramolecules formed using a combination of coordination chemistry and hydrogen bonding.; A series of neutral organoplatinum(IV) complexes were prepared, in which the alkyl groups contained a functional group capable of taking part in hydrogen bonding. These complexes were formed by oxidative addition of reagents RCH 2X to [PtMe2(bu2bipy)], bu2bipy = 4,4 '-di-tert-butyl-2,2'-bipyridine and have the formula [PtXMe2(bu2bipy)(CH2R)]; X = Br, Cl. These complexes formed dimers through O-H...O and N-H...O hydrogen bonding and polymers through N-H...Cl-Pt and O-H...Br-Pt hydrogen bonding.; The above mentioned neutral monoplatinum complexes were further derivatized by addition of AgBF4 or AgPF6, which abstracts the coordinated halide, followed by coordination of a pyridinecarboxylic acid group. These cationic complexes were found to give one-dimensional polymeric, interwoven chain, two-dimensional sheet and multiple ribbon structures through a combination of O-H...O hydrogen bonding between the cation, solvent, or the PF 6 counterion which was found to hydrolyse to PO2F2 - in certain cases.; Methods were employed to synthesize diplatinum(IV) complexes from the monoplatinum(IV) complexes. The use of a silver salt to abstract the coordinated bromide from the complex [PtBrMe2(bu2bipy)(CH2 C6H4CO2H)], followed by coordination of the doubly bridging ligands 4,4'-bipyridine, N,N-bis-pyridin-2-ylmethyl-oxalamide, and N,N-bis-pyridin-4-ylmethyl-oxalamide, results in complexes with one-dimensional polymeric, helical and double helical structures through O-H...O and N-H...O hydrogen bonding.; The reagents ortho-, meta-, and para-dibromoxylene oxidatively added across two platinum atoms of [PtMe2(bu2 bipy)] which, when followed by addition of a silver salt and coordination of a pyridinecarboxylic acid, gave a series of diplatinum complexes with two or more hydrogen bonding functional groups per molecule. One-dimensional polymeric and interwoven chain architectures were obtained.; Organotriplatinum(IV) complexes were made by addition of AgPF6 to the starting monoplatinum(IV) complexes, followed by coordination of the triply bridging ligand s-tris(4-pyridyl)triazine. When the monoplatinum complex [PtBrMe2(bu2bipy)(CH2C 6H4CO2H)] was used, the complex [{lcub}(HO2CC 6H4CH2)(bu2bipy)Me2Pt{rcub} 3{lcub}(mu-NC5H4)3(C3N 3){rcub}][PF6]3, was obtained, the crystal structure of which was found to be the first example of an organometallic polyrotaxane. |
