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First synthesis and characterization of organoplatinum dendritic necklaces and dendritic networks using an outer sphere-outer sphere connection strategy.

机译：首次使用外球-外球连接策略合成和表征有机铂树状项链和树状网络。

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摘要

This thesis described the first report of the use of surface bi-functionalized and tri-functionalized dendrimer subunits as monomers for the construction of three different classes of novel dendrimer-based polymers via an outer sphere-outer sphere connection strategy.; The first part of this thesis illustrated the convergent syntheses and characterizations of a series of surface bi-functionalized dendrimers 116–118 (G1 to G3). Subsequent co-polymerization of these dendritic monomers via their surface acetylene functionalities in the presence of dichlorobis(triethylphosphine)platinum(II) yielded linear organoplatinum dendritic co-polymers (also called dendritic necklaces) 163–165 . Laser light scattering and size exclusion chromatographic analyses revealed that these dendritic necklaces had a very high molecular weight and a high degree of polymerization (up to 880 repeating units). The structure and purity of the precursor molecules as well as those of the dendritic necklaces were examined by 1H-, 13C-, 31P-NMR and UV spectroscopy. The thermal stabilities of the dendritic necklaces were also investigated by thermal gravimetric analysis (TGA). Their thread like morphologies were also characterized by scanning tunneling microscopic (STM) imaging.; The second part of this thesis depicted the co-polymerization of the previously described surface bi-functionalized dendrimers 116–118 in the presence of a small size branching agent 166 with the aim to prepare cross-linking organoplatinum dendritic networks. The [G1]-dendritic network 168 obtained was an insoluble dendritic gel system whose network structure was determined by energy dispersive X-ray and STM techniques. On the other hand, the [G2]- and [G3]-dendritic networks 169–170 were soluble oligomeric systems with little cross-linking. Hence the size (i.e. the generation) of the dendritic co-monomer is an important controlling element in their co-polymerization with the small size tri-platinum(II) co-monomer.; The third part of this thesis described the convergent syntheses and characterizations of surface tri-functionalized dendrimers 174–176 (G0 to G2) as monomers. In contrast to the co-polymerization described in part two, co-polymerizations of these dendritic monomers via their surface acetylene functionalities in the presence of a diplatinum(II) complex 172 successfully produced insoluble organoplatinum dendritic networks 185–187. (Abstract shortened by UMI.)
机译：本论文描述了使用表面双官能化和三官能化树枝状聚合物亚基作为单体通过外球-外球连接构建三种不同类别的新型基于树枝状聚合物的聚合物的第一篇报道。战略。;本文的第一部分说明了一系列表面双功能树状聚合物 116-118 （G1至G3）的收敛合成和表征。这些树枝状单体随后在二氯双（三乙基膦）铂（II）存在下通过其表面乙炔官能度进行共聚，生成线性有机铂树枝状共聚物（也称为树枝状项链） 163– 165 。激光散射和尺寸排阻色谱分析表明，这些树枝状项链具有很高的分子量和很高的聚合度（最多880个重复单元）。用 1 H-， 13 C-， 31 P检验了前体分子和树枝状项链的结构和纯度。 -NMR和UV光谱。还通过热重分析（TGA）研究了树状项链的热稳定性。它们的线状形态也通过扫描隧道显微镜（STM）成像来表征。本文的第二部分描述了在存在小分子支化剂 166 的情况下，上述表面双官能化树枝状聚合物 116-118 的共聚合制备交联的有机铂树状网络。获得的[G1]-树突网络 168 是一种不溶的树突凝胶体系，其网络结构通过能量色散X射线和STM技术确定。另一方面，[G2]-和[G3]-树突网络 169-170 是可溶的寡聚体系，几乎没有交联。因此，树枝状共聚单体的尺寸（，即 generation）是它们与小尺寸三铂（II）共聚单体共聚的重要控制元素。本文的第三部分描述了表面三官能化树枝状聚合物 174–176 （G0至G2）作为单体的聚合合成和表征。与第二部分所述的共聚相反，这些树突状单体通过在其二乙铂（II）配合物 172 存在下通过表面的乙炔功能进行共聚。产生了不溶的有机铂树突网络 185–187 。 （摘要由UMI缩短。）

著录项

  • 作者

    Leung, Cham Fai.;

  • 作者单位

    Chinese University of Hong Kong (People's Republic of China).;

  • 授予单位 Chinese University of Hong Kong (People's Republic of China).;
  • 学科 Chemistry Organic.; Chemistry Polymer.
  • 学位 Ph.D.
  • 年度 2003
  • 页码 p.4356
  • 总页数 290
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;
  • 关键词

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