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Supramolecular Ladder Polymers by Hy...

Ng, Chun Fai.

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Supramolecular Ladder Polymers by Hydrogen-Bonding Mediated Self-Assembly of Organoplatinum(II) Macrocycles.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Supramolecular Ladder Polymers by Hydrogen-Bonding Mediated Self-Assembly of Organoplatinum(II) Macrocycles./
作者:	Ng, Chun Fai.
面頁冊數:	322 p.
附註:	Source: Dissertation Abstracts International, Volume: 77-01(E), Section: B.
Contained By:	Dissertation Abstracts International77-01B(E).
標題:	Organic chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3725374
ISBN:	9781339096193

Supramolecular Ladder Polymers by Hydrogen-Bonding Mediated Self-Assembly of Organoplatinum(II) Macrocycles.
Ng, Chun Fai.

Supramolecular Ladder Polymers by Hydrogen-Bonding Mediated Self-Assembly of Organoplatinum(II) Macrocycles. - 322 p.

Source: Dissertation Abstracts International, Volume: 77-01(E), Section: B.

Thesis (Ph.D.)--The Chinese University of Hong Kong (Hong Kong), 2015.

This thesis reports (a) the synthesis and characterization of quadruple DADA Hbonded oligoamide-based organoplatinum(II) metallomacrocycles 91 and 129, and (b) a synthetic study on the self-assembly properties of the defect-free supramolecular ladder polymers and supramolecular polymers derived from these organoplatinum(II) macrocycles and their precursors.

ISBN: 9781339096193Subjects--Topical Terms:

523952
Organic chemistry.

Supramolecular Ladder Polymers by Hydrogen-Bonding Mediated Self-Assembly of Organoplatinum(II) Macrocycles.
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245 1 0 $a Supramolecular Ladder Polymers by Hydrogen-Bonding Mediated Self-Assembly of Organoplatinum(II) Macrocycles.
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500 $a Source: Dissertation Abstracts International, Volume: 77-01(E), Section: B.
502 $a Thesis (Ph.D.)--The Chinese University of Hong Kong (Hong Kong), 2015.
520 $a This thesis reports (a) the synthesis and characterization of quadruple DADA Hbonded oligoamide-based organoplatinum(II) metallomacrocycles 91 and 129, and (b) a synthetic study on the self-assembly properties of the defect-free supramolecular ladder polymers and supramolecular polymers derived from these organoplatinum(II) macrocycles and their precursors.
520 $a Chapter 1 of this thesis provides background information on metallomacrocycles, Hbond mediated self-assembly and ladder polymers and, in particular, the generation of defect-free supramolecular ladder polymers. In Chapter 2, the syntheses and characterization of the prototype complexes 92, 93 and the targeted rectangular-shaped dinuclear organoplatinum(II) macrocycle 91 are described in detail. A stepwise fragment coupling approach was adopted to access the isomer-free metallomacrocycle 91 from a mono-TIPS-protected bisacetylene 119 and trans-PtCl 2(PEt3)2. The structure and purity of the organoplatinum(II) complex and its precursors were confirmed by 1H, 13 C, 31P NMR, mass spectroscopy and size-exclusion chromatographic analyses. Subsequent physical measurements involving concentration-dependent 1H NMR, two-dimensional NMR (ROESY), viscometry, and dynamic light scattering (DLS) studies were then carried out in Chapter 3 to reveal that macrocycle 91 self-assembled through the pairwise matching of quadruple DADA H-bond arrays to form a supramolecular ladder polymer. The association constant K was determined to be 700 +/- 200 M--1 in 2% CD3OH/CDCl3. Moreover, SEM images of the rectangular metallomacrocycle 91 showed that the compound formed uniform-sized spheres (diameter &sim; 5 mum) with highly folded substructure. DSC analysis also unraveled a higher thermostablity of the structurally perfect supramolecular ladder polymer as compared to those supramolecular polymer analogues formed from its uncyclized precursor 125..
520 $a Chapter 4 of the thesis focuses on the synthesis and self-assembly properties of a trapezoidal organoplatinum(II) macrocycle analogue 129. The synthesis of 129 was readily achieved by Hay homocoupling followed by platinum(II) complexation. The structure and purity of macrocycle 129 and its precursors were characterized by 1H, 13C, 31P NMR, sizeexclusion chromatography and mass spectroscopy. An association constant K of 700 +/- 300 M--1 in 2% CD3OH/CDCl 3 was also determined for the trapezoidal macrocycle 124. The specific viscosity of 124 in 2% CD3OH/CDCl3 was found to be less than that of rectangular 91, but a reversal of trend was observed for the corresponding uncyclized precursor molecules. SEM images of macrocycle 124 also showed the presence of spherical structures similar to those of its rectangular counterpart 91, indicating that the two supramolecular ladder polymers self-assembled via the same mechanism (i.e. H-bonding, alkyl chain inter-digitation and pi--pi stacking) to produce a supramolecular ladder polymer strand which further folded into spherical structures. A comparison of the slightly different self-assembly features of the rectangular 91 vs trapezoidal 129 macrocycles in terms of their molecular geometries was also made.
520 $a Chapter 5 summarizes the key findings in this thesis and suggested future research directions that may broaden our understanding of supramolecular ladder polymers. The thesis is concluded with Chapter 6 which covers the experimental details of the research work.
590 $a School code: 1307.
650 4 $a Organic chemistry. $3 523952
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710 2 $a The Chinese University of Hong Kong (Hong Kong). $3 1017547
773 0 $t Dissertation Abstracts International $g 77-01B(E).
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791 $a Ph.D.
792 $a 2015
793 $a English
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