A series of 2,6- and 3,5-ethynylpyridyl compounds and their cobalt clusters have been prepared and analysed in Chapter 2, in order to study through-space and through-bond interactions between the ethynyl arms. Bidentate N- donor ligands, such as bipyridine and o-phenanthroline with alkyne functionality have been used extensively as building blocks for a wide range of molecular materials, but monodentate ethynylpyridyls have received less attention. The results showed that while there is no orbital restriction on a RC[triple bond]C-n-[pi]�cc-C[triple bond]CR through-bond interaction in 2,6-ethynylpyridyls, no significant interaction exists. Nevertheless, there are intramolecular interactions as manifested in the distortions which occur in the solid state structure of the compounds and the lability of the diphenylphosphine methane (dppm) moieties in the oxidised Co₂(CO)₄dppm species. Polymerisation by Sonogashira coupling between dibromo pyridines or diiodo ferrocene and ethynyl pyridines resulted in only oligomeric fractions that could be separated. The thesis also reports the synthesis and characterization of some novel naphthalimide monomers with acrylic and allyl headgroups. The naphthalimide moiety is substituted in the 4-position with various functionalities. This is presented in detail in Chapter 3 of the thesis. The monomers� structure is the following: [illustration omitted] wherein: A may be a polymerizable group (methacrylate or allyl), which includes a spacer entity (aliphatic or aromatic); B is selected from an ethenyl or ethynyl linked organometallic group, a halogen and/or an amine (i.e. bromo, ethynylferrocene, ethenylferrocene, trimethylsilylethynyl, nitro, piperidine and ethenylpiperidine). The acrylic monomers were synthesized by coupling 4-bromo-1,8-naphthalic anhydride with an amino alcohol to give an imide, which then was coupled with methacryloyl chloride to provide the methacrylate. Functionalization in the 4-position of the naphthalimide moieties was achieved by Sonogashira and Heck coupling reactions with for example ethynylferrocene, trimethylsilyl acetylene, vinylferrocene. For the allyl monomers synthesis, a reaction between allyl amine and 4-Bromo-naphthalic anhydride provided 4-bromo-naphthalimido allyl, which was then functionalized by further Sonogashira and Heck coupling reactions. The monomers were polymerised and copolymerised with other widely used comonomers, such as methyl methacrylate, methyl acrylate, styrene, vinyl carbazole and acrylonitrile. The polymerisation processes and the full analyses of the (co)polymers are described in Chapter 4. Free radical polymerisation, FRP, initiated by azo bisisobutyronitrile, AIBN at elevated temperature was the main technique employed for making the (co)polymers. Atom Transfer Radical Polymerisation, ATRP was conducted for some monomers although the results were inconclusive (the yields were low, under 50%, but the molecular weight distributions were quite narrow, PDI�s <1.7). Heck coupling polymerisation was performed for the bromo- substituted methacrylic and allyl monomers and supplied colorful, well-defined polymeric materials, with low polymerisation degrees. All polymers were analyzed by HPLC, NMR, UV-VIS, IR, electrochemistry and fluorescence. The (co)polymers made by FRP had various molecular masses (Mn = 3000- 90.000), whereas the polydispersities were PDI = 1.4- 4.6. Most of the (co)polymers were fluorescent and had good thermal and electrochemical properties. Potential applications of the polymers have been suggested and relevant literature background in the field is provided in both Chapters 1 and 4. The monomers/ polymers are stable compounds (no special storage conditions required) and can act as good candidates for potential applications in light emitting devices, as resins/ binders for coating materials, in the dyes and pigment industry and also for manufacturing of conducting polymers and/or composite materials.

The work described i n this thesis deals mainly with a fundamental study of two cementation reactions, i.e., Cu(II)/Zn and Co(II)/Zn, using the electrochemical techniques of linear potential sweep voltammetry, cyclic vol tammetry, chronopotentiometry (stripping), capacitance measurements,ring current measurements and impedance spectroscopy. In addition, solution analysis, x-ray diffraction and scanning electron microscopy were employed to achieve a better understanding of the kinetics and mechanisms of the two cementations. The half reactions of the two systems were also investigated as an essential part of the whole study. Of the two systems investigated, the Cu(II)/Zn system, was mainly used as a reference system on which some of the new techniques could be proved. The Cu(II)/Zn reaction has been shown to be diffusion controlled. Five methods, including solution analysis, have been used to determine the rate of reaction. The values of the rate constants thus determined were in good agreement provided allowance was made for the nonstoichiometry of this reaction due to proton displacement by zinc. The Co(II)/Zn cementation reaction, though thermodynamically highly favourable, is kinetically very sluggish. Of the factors affecting this reaction, the solution pH was found to play a substantial role. For example, while the reaction is largely under chemical control, at pH 5 the reaction rate becomes limited by the speed at which cobalt(I1) ions diffuse to the reacting metal surface. The favourable influence of a higher pH on the reduction of cobalt(II) carried out either electrochemically or chemically using zinc powder was ascribed to the increasing formation of the electrochemically active species, CoOH+ . Increasing the temperature also favours the shift from chemical control to diffusion control. Values for the rate constants of the Co(II)/Zn reaction in the absence of added zn2+ ions were determined from Evans' diagram, chronopotentiometry and impedance spectroscopy, The reasons for the differences in the values of rate thus obtained were discussed. The presence of zinc ions in the reaction solution greatly suppressed the rate of Co(II)/Zn cementation reaction. Several factors have been identified as contributing to the reduced reaction rate. These are the double layer effect, zinc ion and hydrogen atom adsorption, and precipitation of basic zinc salts which blanket the reacting metal surface. The action of compounds such as Sb(III) and As(III), which are commonly used to activate the Co(II)/Zn reaction in the presence of large amounts of zn2+, was investigated mainly by impedance spectroscopy. From the similarity of the impedance spectra for the reaction i n the presence of benzoqui none, it was inferred that one role of the activators was to suppress the formation of adsorbed hydrogen on the reacting surface and to allow a higher concentration of the active species, COOH'.

Thesis (M.S.)--Ohio University, June, 1999. / Title from PDF t.p.

Thesis (Ph. D.)--Murdoch University, 1987. / Submitted to the ChemistryProgramme, School of Mathematical and Physical Sciences, Murdoch University.

Thesis (M.Eng)--University of Wollongong, 2006. / Typescript. Includes bibliographical references: leaf 96-106.

Thesis (Ph. D.)--University of Hong Kong, 2009. / Includes bibliographical references (leaves 195-212) Also available in print.

Thesis (M. Phil.)--University of Hong Kong, 2009. / Includes bibliographical references (leaves 74-75) Also available in print.

Thesis (Ph. D.)--Michigan State University. Dept. of Chemistry, 2006. / Title from PDF t.p. (viewed on June 19, 2009) Includes bibliographical references. Also issued in print.

Thesis (M.S.)--West Virginia University, 1998. / Title from document title page. "November 1998." Document formatted into pages; contains ix, 43 p. : ill. (some col.) Includes abstract. Includes bibliographical references (p. 42-43).

Thesis (M.S.)--Worcester Polytechnic Institute. / Keywords: fuel cell. Includes bibliographical references (p. 76).