• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文学位 >Synthesis and characterization of new organic, inorganic, and organometallic tetrathiafulvalenes and cadmium selenide hybrid materials.
【24h】

Synthesis and characterization of new organic, inorganic, and organometallic tetrathiafulvalenes and cadmium selenide hybrid materials.

机译：新型有机，无机和有机金属四硫富瓦烯和硒化镉杂化材料的合成与表征。

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

A variety of new organic, inorganic, and organometallic complexes based on the tetrathiafulvalene (TTF) backbone have been synthesized and characterized for the development of new materials. The organic research of this thesis outlines a novel one-pot synthetic procedure and new purification route for the selective recovery of unsymmetrical TTFs. The advancements regarding this chemistry center around the phosphorus mediated coupling of two different thione heterocycles, and are based on the results of mechanistic studies using {dollar}sp{lcub}31{rcub}{dollar}P NMR. In addition to this, the successful synthesis and characterization of three new classes of tetrathiafulvalenes is presented. These materials may be used for conductive liquid crystals, metal-ion sensor, or high-spin organic materials.; The inorganic chemistry developed in this manuscript presents two firsts in TTF chemistry. The work begins with a synopsis of a new procedure for the selective generation and isolation of tetrathiafulvalene tetrathiolate (TTFS{dollar}sb4sp{lcub}4-{rcub});{dollar} and following the discovery of this ligand synthesis, we succeeded in making the first reported homobimetallic TTFS{dollar}sb4{dollar} inorganic coordination complexes using the late transition metals Pt and Ni. The reactions to produce these complexes were accomplished by introducing TTFS{dollar}sb4sp{lcub}4-{rcub}{dollar} Li{dollar}sp+{dollar}4 to the metal cis-dichlorides {dollar}rm Clsb2Pt(PPhsb3)sb2{dollar}, Cl{dollar}sb2{dollar}Ni(DPPP), and {dollar}rm Clsb2Ni(4,4spprime{dollar}-Mebipy) and subsequently isolating the products. These studies led to the recovery and characterization of first metal-TTF hybrid materials.; As a direct consequence of the difficulties encountered with the late transition metal coordination complexes, we also synthesized the first early transition metal organometallic TTFS{dollar}sb4{dollar} species using the reaction of TTFS{dollar}sb4sp{lcub}4-{rcub}{dollar} Li{dollar}sp+sb4{dollar} with {dollar}rm Clsb2TiRsb2{dollar} (R = Cp, Cp*, i-PrCp). An important result of this research was the first single crystal X-ray structure of a homobimetallic TTFS{dollar}sb4{dollar} complex. In addition to this, these materials proved useful in elucidating the photophysical and electrochemical perturbations resulting from changes in the ligand environment for a given metal. A final application of this class of compounds is that {dollar}rm Cpsb2TiTTFSsb4TiCpsb2{dollar} allows for the divergent approach (via transmetallation) to hetero- and homobimetallic coordination complexes.; As an extension of the work on early transition metal metallocenes we also attempted to make {dollar}rm Cpsb2VTTFSsb4VCpsb2{dollar} complexes in order to study the electronic spin interactions through the TTFS{dollar}sb4{dollar} bridge. However, it was subsequently discovered that the reaction chemistry, on going from Ti to V, was quite different. This led us to explore the synthesis of alkyl substituted vanadocenes to facilitate the recovery of these metal-TTF materials. A major drawback toward accomplishing this goal was the paucity of literature results concerning vanadocene dichlorides. We therefore developed a new, completely general, approach to V based metallocenes, and crystallographically characterized two new complexes.; A final area of research presented in this thesis concerns work undertaken on semiconducting CdSe nanocrystallites, or quantum dots. We developed the first nanocrystallite networks by bridging the CdSe clusters with TTFS{dollar}sb4{dollar}, and subsequently explored the resulting materials photophysical properties. In addition to this we extended the current state of knowledge and postulated a new bonding model concerned with their (CdSe) surfaces using {dollar}sp1{dollar}H NMR. This allowed us to quantify the amount of coverage and what modes of bonding are present, and relate these attributes to the photochemical propertie
机译：已经合成了多种基于四硫富瓦烯（TTF）骨架的新的有机，无机和有机金属配合物，并用于开发新材料。本文的有机研究概述了一种新的一锅法合成方法和新的纯化路线，用于选择性回收不对称的TTF。关于该化学的进展集中在两个不同的硫酮杂环的磷介导的偶联上，并且基于使用{sp} lc {lcub} 31 {rcub} {dollar} P NMR的机理研究的结果。除此之外，还介绍了三种新型四硫富瓦烯的成功合成和表征。这些材料可用于导电液晶，金属离子传感器或高自旋有机材料。本手稿中开发的无机化学代表了TTF化学的两个首次。这项工作首先概述了选择性生成和分离四硫富瓦烯四硫醇盐（TTFS {dollar} sb4sp {lcub} 4- {rcub}）; {dollar}的新程序，在发现这种配体合成后，我们成功地使用后期过渡金属Pt和Ni制备了第一个报告的同双金属TTFS {dolb} sb4 {dollar}无机配位化合物。通过将TTFS {dollar} sb4sp {lcub} 4- {rcub} {dollar} Li {dollar} sp + {dollar} 4引入金属顺式二氯化物{dol} rm Clsb2Pt（PPhsb3）sb2中来完成生成这些复合物的反应。 {dollar}，Cl {dollar} sb2 {dollar} Ni（DPPP）和{dollar} rm Clsb2Ni（4,4spprime {dollar} -Mebipy），然后分离产物。这些研究导致了第一种金属-TTF杂化材料的回收和表征。作为后期过渡金属配位化合物遇到困难的直接结果，我们还利用TTFS {dollar} sb4sp {lcub} 4- {rcub的反应合成了第一个早期过渡金属有机金属TTFS {dollar} sb4 {dollar}物种} {dol} Li {dollar} sp + sb4 {dollar}和{dol} rm Clsb2TiRsb2 {dollar}（R = Cp，Cp *，i-PrCp）。这项研究的重要结果是同双金属TTFS {dollar} sb4 {dollar}配合物的第一个单晶X射线结构。除此之外，这些材料被证明可用于阐明由给定金属的配体环境变化引起的光物理和电化学扰动。这类化合物的最终应用是{dol} rm Cpsb2TiTTFSsb4TiCpsb2 {dollar}允许通过异金属和同双金属配位化合物（通过跨金属化）进行分歧。作为对早期过渡金属茂金属的研究的扩展，我们还尝试制备{dol} rm Cpsb2VTTFSsb4VCpsb2 {dollar}络合物，以研究通过TTFS {dollar} sb4 {dollar}桥的电子自旋相互作用。但是，随后发现从Ti到V的反应化学是完全不同的。这促使我们探索烷基取代的钒钒烯的合成，以促进这些金属-TTF材料的回收。实现该目标的主要缺点是缺乏关于二氯钒二烯的文献结果。因此，我们开发了一种新的，完全通用的基于V的金属茂的方法，并在晶体学上表征了两种新的配合物。本文提出的最后一个研究领域涉及半导体CdSe纳米微晶或量子点的研究。我们通过将CdSe团簇与TTFS {dollar} sb4 {dollar}桥接来开发了第一个纳米晶体网络，随后探索了所得材料的光物理性质。除此之外，我们利用{sp} {1} H NMR扩展了当前的知识水平，并提出了一个有关其（CdSe）表面的新键合模型。这使我们能够量化覆盖量和存在的键合模式，并将这些属性与光化学特性相关联

著录项

  • 作者

    Belot, John Allen, Jr.;

  • 作者单位

    Carnegie Mellon University.;

  • 授予单位 Carnegie Mellon University.;
  • 学科 Chemistry Inorganic.; Chemistry Organic.; Physics Condensed Matter.; Engineering Materials Science.
  • 学位 Ph.D.
  • 年度 1995
  • 页码 178 p.
  • 总页数 178
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 无机化学;有机化学;工程材料学;
  • 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