Di-2-pyridinylmethanone (di-2-pyridyl ketone) is a well-known ligand within the family of basic building blocks for the construction of metal-organic complexes with diverse architectures and potential applications in relation to their physical and chemical properties. A systematic investigation on the generation and structure of transition metal complexes based on six ligands containing the dipyridinylmethanone moiety is reported in this thesis. Although all these ligands are known except L7, their coordination chemistry remains unexplored to date. / Ligand 2-pyridinyl-3-pyridinylmethanone (L1) is an excellent building block for the construction of infinite single-strand helical architectures with various metal salts. In the resultant helical complexes, Ll exhibits three kinds of coordination modes involving two kinds of bridging conformations, resulting in four types of single-strand helical chains. Among them is a pair of helical conformational polymorphs generated by the solvent-controlled process, in which the 21 helices of opposite chirality in one are stacked alternately to form a racemate, whereas the 41 helices in the other are assembled homochirally by inter-chain argentophilic interaction to generate a conglomerate. In a series of six isostructural 21 helical Ag(I) complexes, the pitch length corresponds not only to the size of the embedded anion but also to the manner of its fitting into the groove of the helix. In the Co(II) and Zn(II) complexes that comprise helical chains without anion embedment, the pitch lengths are dictated by the size of the metal cations. / Ligand 2-pyridinyl-4-pyridinylmethanone (L2) readily gives rise to dimeric metallacyclophanes with various Ag(I) salts, which bear close structural similarity. An ordered sequence of the coordinating ability of a series of nine polyatomic monoanions has been established on the basis of structural parameters derived from their interaction with a common disilver(I) metallacyclophane skeleton in isostructural complexes. The reactions of L2 with Co(II), Cu(II), Zn(II) and Cd(II) salts give rise to supramolecular architectures assembled through weak interactions including hydrogen bonding and pi···pi stacking, in which L2 adopts various ligation modes. / Metal complexes of 3-pyridinyl-4-pyridinylmethanone (L4) exhibit a variety of structural types: single chain, ladder-like chain, (4,4) network and tetrameric unit. (Abstract shortened by UMI.) / Chen Xudong. / "July 2005." / Adviser: Thomas C. W. Mak. / Source: Dissertation Abstracts International, Volume: 67-07, Section: B, page: 3787. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (p. 143-164). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract in English and Chinese. / School code: 1307.
| Identifer | oai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_343711 |
| Date | January 2005 |
| Contributors | Chen, Xudong., Chinese University of Hong Kong Graduate School. Division of Chemistry. |
| Source Sets | The Chinese University of Hong Kong |
| Language | English, Chinese |
| Detected Language | English |
| Type | Text, theses |
| Format | electronic resource, microform, microfiche, 1 online resource (xi, 180 p. : ill.) |
| Rights | Use of this resource is governed by the terms and conditions of the Creative Commons “Attribution-NonCommercial-NoDerivatives 4.0 International” License (http://creativecommons.org/licenses/by-nc-nd/4.0/) |
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