• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文学位 >Novel oligomeric and polymeric materials based upon the dibenzotetraaza[14]annulenes.
【24h】

Novel oligomeric and polymeric materials based upon the dibenzotetraaza[14]annulenes.

机译：基于二苯并四氮杂[14]环烯的新型低聚物和聚合物材料。

获取原文
获取原文并翻译 | 示例
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

The class of compounds known as the dibenzotetraaza[14]annulenes have been of particular interest over the past 25 years, with the initial impetus for research being the relationship they hold with the naturally occuring porphyrins.The main aim of the work undertaken was to establish the potential of dibenzotetraaza[14]annulene type systems for the development of novel materials whose applicable behaviour was likely to fall into one of the following three categories; liquid crystals, organic conductors, and chelating systems. Additionally the chemistry involved with the synthesis of these types of materials was interesting in its own right and provided a platform for the author to increase his own knowledge of chemistry. The research undertaken may be broadly classified into the following areas: 1. The preparation of linear Schiff base polymers, 2. The preparation of dibenzotetraaza[14]annulenes (metal complexes and free ligands), 3. The preparation of 1-D and 2-D unsymmetrical macrocyclic complexes, and 4. The preparation of polymeric materials incorporating dibenzotetraaza[14]annulenes both as part of the polymeric backbone and as pendant side chains in a comb type polymer. 1. The preparation of linear Schiff base polymers. The Schiff base condensation of phenylenediamines with malondialdehydes has enabled the preparation of materials of the type illustrated below. [chemical formula]. Examination of the materials by differential scanning calorimetry has shown that many of the materials exhibit interesting thermal transitions from one crystalline state to another. However the use of thermal microscopy has not shown any of these phases to be liquid crystalline transitions. 2. The preparation of dibenzotetraaza[14]annulenes (metal complexes and free ligands). An extensive array of dibenzotetraaza[14]annulenes have been prepared, generally by a one step process involving the reaction of ortho-phenylenediamine and various 2-substituted malondialdehydes in the presence of a suitable acid catalyst and solvent. [chemical formula]. 3. The preparation of 1-D and 2-D unsymmetrical macrocyclic complexes. The introduction of unsymmetricality into the dibenzotetraaza[14]annulenes has been of interest since dipole-dipole interactions between molecules may lead to enhanced crystalline stacking, which in turn has a direct effect on any liquid crystalline or semiconducting properties the material may exhibit. Consequently the preparation of unsymmetrical dibenzotetraaza[14]annulenes has been undertaken, which has often required extended stepwise synthetic reaction pathways involving the use of protecting reagents. Small quantities of pure materials have been prepared and are believed to be the first of their type. 4. The preparation of polymeric dibenzotetraaza[14]annulenes. The incorporation of dibenzotetraaza[14]annulenes into a polymeric system has been examined in two ways. The initial study concentrated on the incorporation of the macrocycle directly into the polymer backbone and involved the reaction of suitably functionalised dibenzotetraaza[14]annulenes with linking groups such as para-phenylenediamine. The additional study has focussed on a method of forming polymers which include the macrocyclic complexes as pendant side chains in a comb type polymeric arrangement (illustrated below). [chemical formula]. At present the prepartion of a polymer of this type has not been achieved. However an extensive study into the attachment of groups to the macrocycles which are capable of undergoing polymerisation has been undertaken which has established the potential use of the Gabriel synthesis of amines and the Wittig reaction as potential methods of attachment.
机译：在过去的25年中，二苯并四氮杂[14]环戊二烯一类化合物特别受关注，最初的研究动力是它们与天然存在的卟啉的关系。研究的主要目的是确定二苯并四氮杂[14]环戊烯型体系开发新型材料的潜力，该新型材料的适用行为可能属于以下三类之一；液晶，有机导体和螯合系统。另外，与这些类型的材料合成有关的化学本身很有趣，并为作者提供了一个增加自己的化学知识的平台。所进行的研究可大致分为以下几个方面：1.线性席夫碱聚合物的制备； 2.苯并四氮杂[14]环戊烯（金属配合物和游离配体）的制备； 3.一维和2的制备-D不对称大环配合物，和4.结合有二苯并四氮杂[14]环烯作为聚合物主链的一部分和梳型聚合物侧链的侧链的聚合物材料的制备。 1.线性席夫基础聚合物的制备。苯二胺与丙二醛的席夫碱缩合反应使得制备以下所示类型的材料成为可能。 [化学式]。通过差示扫描量热法对材料的检查表明，许多材料表现出令人感兴趣的从一种晶态到另一种晶态的热转变。然而，热显微镜的使用并未显示出这些相中的任何一个都是液晶转变。 2.二苯并四氮杂[14]环戊烯（金属配合物和游离配体）的制备。通常通过一步法，包括在适当的酸催化剂和溶剂存在下，使邻苯二胺与各种2-取代的丙二醛反应，制备了各种各样的二苯并四氮杂[14]环戊烯。 [化学式]。 3.一维和二维不对称大环配合物的制备。将不对称性引入二苯并四氮杂[14]环烯中引起人们的关注，因为分子之间的偶极-偶极相互作用可能会导致增强的晶体堆积，进而直接影响该材料可能呈现的任何液晶或半导体特性。因此，已经进行了不对称二苯并四氮杂[14]环戊烯的制备，这经常需要扩展的逐步合成反应途径，包括使用保护剂。已经制备了少量的纯净材料，并且被认为是它们的第一类型。 4.制备聚合二苯并四氮杂[14]环烯。已通过两种方法研究了将二苯并四氮杂[14]环烯掺入聚合物体系中。最初的研究集中在将大环化合物直接掺入聚合物主链中，并涉及适当官能化的二苯并四氮杂[14]环烯与连接基团（例如对苯二胺）的反应。另外的研究集中在形成聚合物的方法上，该聚合物包括大环配合物作为梳型聚合物排列中的侧链侧链（如下所示）。 [化学式]。目前还没有实现这种聚合物的预配。然而，已经进行了对基团与能够进行聚合的大环的连接的广泛研究，这已经确定了加百利胺的合成和维蒂希反应作为潜在的连接方法的潜在用途。

著录项

  • 作者

    Challoner, Nicholas Ian.;

  • 作者单位

    Sheffield Hallam University (United Kingdom).;

  • 授予单位 Sheffield Hallam University (United Kingdom).;
  • 学科 Organic chemistry.
  • 学位 Ph.D.
  • 年度 2000
  • 页码 266 p.
  • 总页数 266
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号