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新型含N、S、O配体的超分子金属配合物的合成及晶体结构

Synthesis and Crystal Structure of New Supramolecular Metal Complexes with Nitrogen, Sulfur and Oxygen Atoms

【作者】 王祥

【导师】 罗芳;

【作者基本信息】 东北师范大学 , 无机化学, 2008, 硕士

【摘要】 金属配位聚合物及超分子研究不仅是沟通有机和无机超分子研究的桥梁,而且集理论基础与应用基础研究于一体。近年来,这一领域成为材料科学和化学学科中最活跃的研究领域之一,并处于高速发展的关键时刻。利用共价键所构筑的配位聚合物已经受到人们的广泛研究,该体系具有稳定、刚性、较易预测和操控等特点。近期研究也表明,高度一致或有序的非共价键弱作用力(如氢键)的结合所产生的超分子体系也可以具有相当的稳定性,而且,非共价体系具有柔软、可调控、可逆等特点。对这些新型体系结构和性能的研究不仅可以丰富合成化学的理论与实验研究,而且还将进一步拓展其在电子、光学、磁化学、催化以及生物模拟等诸多领域的广阔应用前景。近年来,由于水簇与生物体系及化学过程存在着重要的关联,因此在实验和理论研究上均倍受关注。各种水簇的结构参数对于处在分子阶段的体积水的性质能够得到精确的描述有着可观的预期。这些聚合物的水形态在结构上处于水簇和体积水之间,与体积水有相近的性质。因此对于水簇的研究,不论对水结构的进一步理解,还是提供更新的水表结构有着重大的意义,而且也为水与生物体系之间存在的重要关系有着更新的、进一步的研究暗示。本文首先合成新的含氮、含氧配体4,5-二氮杂芴-9-[3,5-二羧基]苯亚胺(dafdc)和含硫配体4,4’-二硝基二苯乙烯-2,2’-二磺酸(DNS),然后利用常规方法成功地合成了如下配合物:含有螺旋金属-水簇链的超分子配合物[Mn(dafdc) (H2O)4]·7H2O;新型DNS配体与金属镍的超分子配合物[Ni(H2O)6](DNS)·2H2O;二苯胺磺酸钠(dpas)、乙二胺与金属镍的二维网状超分子配合物[Ni(en)2](dpas)2。配合物结构和组成通过X-射线衍射、FT-IR和元素分析等测试手段进行了表征。

【Abstract】 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 the ionophore chemistry, ion pair extraction chemistry, phase transfer catalysis chemistry 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-interpenerating open networks with variable cavities or channels of desire size, or well entangled structures through interpeneration.Water clusters have been intensively investigated both experimentally and theoretically due to their important relevance to biological systems and chemical processes. Their structural information holds considerable promise for achieving a more accurate description of the properties of bulk water at a molecular level. These polymeric water morphologies, which structurally lie in between water clusters and bulk water, have physical properties very closely associated with those of bulk water. Without doubt, the above studies have significantly advanced the understanding of water structures and provided novel structural aspects of water and new insights into water with implications for biological environments.In this paper, the new ligands of 3,5-(4,5-Diazafluoren-9-ylideneamino)benzoic acid(dafdc) and 4, 4′-Dini-trostilbene-2, 2′-Disulfonic Acid(DNS) with nitrogen sulfur and oxygen Atoms were synthesized. Then the follows new supramolecular metal complexes were synthesized by conventional method.The supramolecular complexes with infinite metal-water clusters chain of [Mn(dafdc) (H2O)4]·7H2O;The supramolecular complexes with new DNS of [Ni(H2O)6](DNS)·2H2O; The metal complexes with sodium diphenylamine sulphonic acid salt(dpas) of [Ni(en)2](dpas)2;The crystal structure and composition of the complexes were confirmed by X-ray single crystal diffraction and infrared spectrum and elemental analysis.

【关键词】 配位聚合物超分子氢键水簇
【Key words】 complexessupramolecularhydrogen bondwater cluster
  • 【分类号】O641.4
  • 【被引频次】1
  • 【下载频次】177
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