4-酰基吡唑啉酮衍生物与咪唑、2,2'-联吡啶、4,4'-联吡啶混配超分子配合物的合成、表征和晶体结构
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摘要
近年来,超分子配合物因在催化化学、主客体-超分子化学和分子磁性材料、超导材料、非线形光学材料等方面的潜在应用价值而成为最活跃的研究领域之一。然而有关4-酰基吡唑啉酮衍生物与咪唑、多吡啶类混配超分子配合物方面的工作还尚未开展,而且这方面的研究国内外仍鲜有报道。因此,4-酰基吡唑啉酮衍生物与第二配体相结合的混配超分子配合物的合成、研究对超分子配合物的开发与应用有着重要的意义。
     本论文主体部分以4-酰基吡唑啉酮的四种衍生物为主要分子骨架,分别引入咪唑、2,2′-联吡啶、4,4′-联吡啶作为第二配体,合成了三类超分子配合物,通过元素分析,热重差热分析和红外分析确定了配合物的组成和结构,并对部分配体及其配合物的抑菌活性进行了初步探讨。全文共分四章。
     第一章,1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮缩对硝基苯甲酰肼(PMBP-PNBH),1,3-二苯基-4-乙酰基-吡唑啉酮缩水杨酰肼(DPAP-SHZ)为第一配体,咪唑为第二配体合成了两个系列的超分子配合物,通过元素分析,热重-差热分析,红外光谱分析和单晶X-射线衍射等分析手段对其进行了表征,确定了混配配合物组成和结构。并对部分配体及配合物的抑菌活性进行了初步探讨。晶体结构分析结果表明,生成的配合物中除了[Zn(PMBP-PNBH)Im]_2为双核混配配合物外,其它均为单核混配配合物。
     第二章,以1,3-二苯基-4-乙酰基-吡唑啉酮缩水杨酰肼(DPAP-SHZ)为第一配体,2,2′-联吡啶为第二配体,合成了一个系列超分子配合物,通过元素分析、热重差热分析、红外光谱和X-射线单晶衍射分析确定了配合物组成和结构。结果表明在该类配合物中,Ni、Zn的配合物为六配位畸变的八面体构型单核混配配合物,配体DPAP-SHZ失去两个质子以负二价三齿参与配位,2,2′-联吡啶作为中性二齿配体参与配位和一个配位的溶剂甲醇分子。Cu的配合物则为五配
With the rapid growth in supramolecular chemistry in recent years, a great deal of effort has been devoted to the design and assembly of supramolecular compounds, for these compounds have potential applications in catalyses, molecular recognition, molecular electronics, photonic materials and so on. Moreover, the syntheses of various supramolecular compounds help to obtain new information of intermolecular interactions, which is apparently important for rational design and construction of new framework structures. Currently, a lot of researchers are focusing their attention on the crystal engineering of supramolecular architectures organized by coordinate covalent bonds or hydrogen bonds andπ-πstacking interactions. In particular, the hydrogen bonding has attracted most interest due to its relative strength and directionality in generating a great variety of one-(1-D), two-(2-D), and three-dimensional (3-D) either non-interpeneratiog open networks with variable cavities or channels of desire size, or well entangled structures through interpeneration.
     Pyrazolone and its derivatives form an important class of such compounds and have attracted considerable scientific and applied interest. Pyrazolones, especially 4-acyl-pyrazolone, display several different coordination modes with respect to classicalβ-diketonates . Therefore, the 4-acyl-pyrazolone derivatives are broadly used in many fields, especially in biological, clinical and analytical applications. The flexibility and conformational freedom of 4-acetyl-pyrazolone ligands give rise to a variety of interesting structural motifs. In our previous work, we have synthesized a series of 4-acyl-pyrazolone derivatives and reported several transition metal complexes, but no detailed studies on complexes containing 4-acetyl-pyrazolone and
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