发布时间 : 星期一 文章刚性共轭富烯配体及其超分子聚集体的合成、结构和性质的研究更新完毕开始阅读05c1a6c408a1284ac850431c
单位代码 10445 学号 991175 分类号 O621.3
硕 士 毕 业 论 文
和性质的研究
专业名称： 有机化学 研究生： 靳 国 霞 指导教师： 董育斌 教授
2002年4月
刚性共轭富烯配体及其超分子聚集体的合成、结构
摘要
以自组装战略为基础的有机－无机配位超分子聚合物化学是目前国际化学界最活跃、最前沿的研究领域之一，亦是合成新型纳米级有机－无机复合功能材料的最有效的途径之一。寻找具有新颖结构及功能的有机配体是合成具有新奇结构及物化性质的复合超分子聚集体的关键。基于此，我们合成了一系列刚性共轭的纳米级富烯类配体，并以之与过渡金属离子反应合成了同时基于金属－碳和金属－杂原子两种键合作用的有机－无机配位高聚物及以氢键作用为驱动力的超分子聚集体。
我们利用含芳香取代基的环戊二烯基负离子与含-CN、-I、-CO2CH3等配位有机基团的芳酰氯反应成功地合成了17个既含芳香基团又含杂原子配位基团的刚性共轭富烯类配体。除用元素分析，1HNMR及IR表征其结构外，尚用X－射线衍射法测定了5个代表物的单晶分子结构。单晶结构与谱学数据表明，该类化合物以富烯的形式存在, 两个芳酰基处于环戊二烯环的邻位，其中烯醇式羟基（δ
OH＝17.71-18.33
ppm）与羰基氧通过分子内氢键形成七
员环，单晶结构表明两个芳酰环与氢键七员环不共平面。
用所合成富烯类配体与AgSO3CF3反应，合成了2个结构新颖的配位聚合物[Ag2(L1)(H2O)2 (SO3CF3)2]·0.5C6H6（18）和Ag4(L2)2(H2O)2 (SO3CF3)4(η
1
- C6H6)（19）。化合物18－19提供了第一例同时基于Ag-N和Ag-C协同键
合作用的有机－无机配位聚合物。18的结构为一维孪生链通过强的分子间氢键形成的二维网状结构，结构中存在很大的孔穴（21×15 ?），客体苯分子占据其中。在固态下，19的结构为含金属大环的一维链, 值得指出的是19中存在两种形式的Ag-C键：η1-C6H6-Ag和η2-Cp-Ag。
用所合成刚性多齿有机配体与过渡金属Cu2+、Co2+、Mn2+的醋酸盐反应，分别合成了含七员金属环的配合物（20－22），在固态下，20－22为分子间氢键(N…H－O)驱动的一维链状超分子聚集体。
研究表明，在固态下，所合成刚性共轭富烯类有机配体及有机－无机复合超分子聚集体均具有荧光性质；而且通过将金属离子引入聚合物不仅改变了有机配体分子的发光波长，亦对其发光强度有影响。
关键词：自组装 有机－无机配位聚合物 超分子聚集体 富烯配体 七员
金属环
Syntheses, Structural Characterization
and Luminescent Properties of Supramolecular Complexes Generated from New Type of Conjugated Fulvene
Ligand
Department of Chemistry, Shandong Normal University
Jinan 250014, P. R. China
Major: Organic Chemistry Author: Guo-Xia Jin
Supervisor: Prof. Yu-Bin Dong
April 24, 2002
Abstract
The chemistry of organic-inorganic coordination polymers or supramolecular architectures has recently become area of increasing interest. Self-assembly of organic ligands and inorganic metal ions is one of the most efficient and widely used approaches for the construction of organic-inorganic composite materials. So far, among the many diverse efforts to find key factors in the development of polymeric compounds with novel structures and physical-chemical properties, the dominant synthetic strategy has been to select different organic ligands with specific geometry and functional groups. In the thesis, we wish to report the synthesis and structures of a series of new type rigid conjugated nanometer-sized fulvene ligands, and coordination polymeric compounds based on both metal-carbon
and
metal-heteroatom
interactions
and
also
H-bonded
supramolecular architectures generated from this new type of fulvene ligands. Totally 17 new type of fulvene ligands have been synthesized by the reaction of substituted-benzoyl chloride with Cp and substituted Cp anions. All the new compounds are fully characterized by infrared spectroscopy, 1H NMR and elemental analysis, as well as for 5 represenatives by single-crystal X-ray diffraction methods. The structure analysis reveals that this new type of ligand exists in the form of fulvene, the two aroyl groups on the Cp or substituted-Cp ring are adjacent, the enol hydrogen atom (the proton resonance as singlet in the range of 17.71-18.33 ppm) is hydrogen bonded to the neighbor carbonyl oxygen atom (IR (C=O) in the range of 1610－1630cm-1) to form a hydrongen bonded seven-membered ring. In addition, the two aroyl rings are not in the same plane with the seven-membered ring.
Two novel Ag-containing polymeric compounds, namely [Ag2(L1)(H2O)2(SO3 CF3)2]·0.5C6H6 (18) and Ag4(L2)2(H2O)2(SO3CF3)4(η1-C6H6) (19) have been successfully synthesized by combination of the fulvene-typed organic spacers with AgSO3CF3 in the solution. To our knowledge, compounds 18 and 19 reported herein represent the first example of organic-inorganic composite polymers based on both Ag-N and Ag-C coordination interactions. In the solid state, compound 18 features a one-dimensional double chain motif. These