含功能基团配合物的分子设计、合成、结构及性质研究

【作者】 张宣军；

【导师】 田玉鹏； Fun Hoong Kun； 谢复新；

【作者基本信息】 安徽大学 ， 无机化学， 2001， 硕士

【摘要】 论文在大量文献调研基础上，总结了羧酸根不同配位方式及结构变化多样的羧酸配合物的合成条件和性质研究；对咔唑、吩噻嗪类衍生物优良的光学、光电转换性质研究进展进行了较为详细的总结。我们设想把这些功能性的基团通过修饰引入到无机分子中，利用无机物熔点高、机械强度大、物化稳定性好等优点结合有机化合物良好的非线性光学性质、光电转换性质、分子的可剪接性等优点，探索合成新型的有机-无机杂化材料。在论文工作中，主要设计合成了咔唑乙酸及其金属配合物和吩噻嗪衍生配合物，并对其磁性质、电化学性质、光致发光性质进行了研究；在分子间以S...S作用形成超分子的合成方面也做了一些初步工作。论文的主要工作总结如下：1．探索了合成咔唑乙酸的新方法，并把产率提高到92％。（目前由一步反应合 成咔唑乙酸的文献最高产率49％）。2．通过设计和组装，合成了一系列双核和单核咔唑乙酸Cu（Ⅱ）-Cu（Ⅰ）、Zn（Ⅱ）、 Cd（Ⅱ）、Fe（Ⅲ）、Ca（Ⅱ）、Mg（Ⅱ）配合物。该系列配合物中有九种新化合物的 晶体结构通过单晶X衍射法解出。3．研究了形成单核和双核配合物的影响因素，结果表明，溶剂碱性增强和第 二配体的加入有利于配合物由双核向单核转变。4．配合物的电化学性质研究表明：配合物Cu₂（RCOO）₃（phen）₂ClO₄在DMF溶 液中发生一个双电子氧化-还原和两个单电子氧化-还原，而CU₂（RCOO）₄L₂只 发生两个单电子转移。由此可以得出Cu₂（RCOO）₃（phen）₂ClO₄在DMF溶液中 保持与固态下同样的双核结构，而Cu₂（RCOO）₄L₂在溶液中是以与固态双核 结构不同的单核形式存在。5．对d¹0结构的Zn（Ⅱ）、Cd（Ⅱ）、Cu（Ⅰ）以及Ca（Ⅱ）、Mg（Ⅱ）的咔唑乙酸配合物的 光致发光性质进行了研究，结果表明该类化合物都具有良好的固体发光性　 质。从荧光谱图上可以看到，不但有配位单体的发射，还有不同于单体的激 予徽人学硕士学位论文”“”二00一届”“”张亘军 激基缔合物和激基复合物的发射，而且还得到了单体发射与激基缔合物或激 基复合物发射共存的复合发光，这在新型发光材料的合成方面做了较有意义 的探索。6．通过分子设计，合成了一系列吩噬嗓衍生配合物。NIL’。的晶体结构通过单 晶X衍射浩解出，在结构空间中，分子间通过S．．石作用形成超分子。 论文最后对工作进行了总结，提出了一些不足之处及工作的展望。更多还原

【Abstract】 Based on detailed investigation of a great deal of related literature, I reviewed the different coordination modes of carboxylato group, the synthesis methods and property studies of a large variety of carboxylates as well as the recent progress in this field. The property studies and applications of carbazole and phenothiazine derivatives are also reviewed. Inorganic compounds possess good qualities such as high melting point, physical and chemical stability as well as the merits of organic compounds such as novel optical and electronic properties and convenience for molecule design. It is assumed that it must be significant to introduce the functional groups such as carbazole and phenothaizine into inorganic molecules to explore organic-inorganic hybrid materials with novel properties. Based on this consideration, a great deal of work have been done on the molecule design and synthesis of N-carbazolylacetic acid and its complexes with metal ions. Except the binuclear copper complex with strong antiferromagnetic interaction we also obtained a series of d10 and Ca(II), Mg(II) complexes with strong photoluminescence. The main achievements in my work are summarized as follows: 1. N-carbazolylacetic Acid was synthesized by a new method in high yield(92%), which was much higher than those in literatures hitherto. 2. By molecule design and assembly, we synthesized a series of N.carbazolylacetates. In this series of compounds, the structures of nine kind of new complexes were determined by X-ray analysis. 3. We studied the factors influencing on the formation of binuclear and mononuclear complexes. We found that mononuclear complexes were easily formed when the solvent is a strong base or when excess of other ligand was introduced. 4. The electrochemistry of copper complexes were studied. From the cyclicvoltammetry curves, we observed that complex Cu2(RCOO)3(phen)2 C104(hereafter abbreviated as BtETCC) exhibits binuclear formation in DMF solution as well as in solid state, whereas C?RCOO)4L~ (hereafter abbreviated as BCTCF) exhibits mononuclear formation which is different from the binuclear formation in solid state. 5. d10 and M(II) complexes(M Ca and Mg) derived from N-carbazolylacetic acid exhibit strong - photoluriiinescence at different wavelengths. From the fluorescence spectra we observed the emissions of the monomer and the excimer or exciplex. 6. By molecule design, we-synthesized a series of complexes derived from Schiff base containing phenothaizine. The structure of complex NiL? was determined by X-ray analysis. In the crystal lattice, the molecules are governed by S... S contact leading to supramolecule. At last, the whole work has been summarized and the prospective following these work in the present thesis are suggested.更多还原