【作者】 孙茜；

【导师】 高恩庆；

【作者基本信息】 华东师范大学 ， 物理化学， 2009， 博士

【摘要】 配位聚合物在多孔、催化、光、电、磁学等方面具有潜在的应用价值,是当今化学、材料科学、生命科学等领域的研究主流和热点课题之一。本论文在配位聚合物晶体工程的指导下,分别以刚性的多元芳香族羧酸对苯二丙烯酸（H₂ppda）、间苯二丙烯酸（H₂mpda）和均苯三苯烯酸（H₃BTA）为桥联配体,同过渡金属离子或者稀土金属离子配位组装,并引入螯合端基配体或联吡啶类中性桥联配体进行结构调控,构筑26个新颖的一维、二维、三维配位聚合物,在晶体结构分析的基础上研究了部分配位聚合物的磁性和热稳定性。研究工作主要分为以下几个部分:1.以二元芳香羧酸类配体构筑的配位聚合物及其磁性研究:（1）以ppda为桥联配体,分别同过渡金属离子Mn（Ⅱ）、Fe（Ⅱ）、Co（Ⅱ）合成了一系列同晶的配位聚合物,羧基采用syn-anti的配位方式将金属离子连接成二维层,层间通过配体连成三维柱层结构。以mpda为桥联配体,分别与金属离子Mn（Ⅱ）、Co（Ⅱ）组装得到两个同晶的配位聚合物,同样具有金属离子与羧酸桥联的二维层,但配体另一端质子未脱落,没有扩展成三维结构,层与层之间通过氢键连接。磁性测试表明金属—羧基桥联的二维层内反铁磁耦合居主导地位,低温下配合物1和2表现为自旋倾斜引起的弱铁磁性,临界温度分别为3.8K和4K。值得一提的是以二价金属离子Fe（Ⅱ）与单一羧基桥联的此类配位聚合物文献中还未见报道。（2）以mpda为桥联配体,在溶剂热条件下同稀土金属离子Nd（Ⅲ）配位组装,溶剂DMF原位分解生成甲酸并参与配位,得到一个由甲酸和mpda共同成桥的三维配位聚合物。该化合物具有新颖的（4·6²）₂（4²·6）(4⁷·6⁴·8¹⁰)拓扑结构。我们对该配合物进行了光谱学表征,热稳定性分析,并对其磁性进行了定性分析。2.以二元芳香羧酸构筑Zn（Ⅱ）与Cd（Ⅱ）的配位聚合物:选择取向不同的二元苯丙烯酸H₂ppda与H₂mpda为桥联配体,采用水热和溶剂热以及常温下液相扩散,模板剂诱导等不同的合成技术,共得到六个Zn（Ⅱ）和Cd（Ⅱ）的配位聚合物（7-12）,对它们进行了晶体结构分析。其中配合物9-12有相同的化学式,但是空间上的结构却大相径庭,有螺旋链,之字链,也有三维结构。从超分子构筑的角度上分析,它们都属于三维“柱层结构”,层内都有螺旋结构产生,最有趣的是经由不同构型的配体传递的螺旋方向不同,从而使晶体结构有手性与非手性之分。文中我们对这一现象进行了详细的阐述,并对配合物的空间群、配位构型、氢键层特征、配体构型和配合物结构等进行讨论。3.螯合端基配体调控的苯二丙烯酸配位聚合物:以ppda和mpda为桥联配体,以螯合端基配体邻菲哕啉（phen）或2,2’-联吡啶（2,2’-bpy）为辅助配体,与过渡金属离子配位组装得到六个一维或二维的低维配位聚合物,分别对它们进行光谱学表征和晶体结构研究,从晶体工程角度探讨了螯合型辅助配体的引入对超分子自组装的影响,尤其是π-π堆积、氢键等分子间作用力在超分子结构构筑中发挥的作用。研究了部分配合物的磁性,并研究了部分配合物的骨架热稳定性。4.中性桥联配体调控的苯二丙烯酸配位聚合物:以ppda和mpda为桥联配体,利用长短不同及刚柔结合的原则,选择不同的联吡啶类中性桥联配体同过渡金属离子配位组装得到一系列新颖的配位聚合物,分别对它们的结构进行分析和表征,研究了配合物的热稳定性。其中值得一提的是我们利用mpda配体与桥联配体bpea/bpee/bpp分别构筑的一系列Zn（Ⅱ）的配位聚合物,拓扑学上都可视为混合配体桥联的（4,4）二维格子,因为桥联型辅助配体存在长短和刚柔差异而导致配位聚合物分子在空间堆积和网格贯穿方式上有所不同,文中较为详尽地探讨了结构的变化规律和配体构型的影响因素。5.基于均苯三丙烯酸为配体构筑配位聚合物:以H₃BTA为桥联配体,利用SBU策略和网络设计合成策略,同过渡金属离子Mn（Ⅱ）、Cd（Ⅱ）分别配位组装,得到两个三维的多孔配位聚合物骨架,对它们进行了光谱学表征和晶体结构分析,研究了部分配位聚合物的骨架稳定性和磁性。其中配合物26是基于七核盘状SBU和BTA构筑的MOF骨架,对其结构进行了拓扑分析,为罕见的3,18-连接的（4²·6）₆(4³⁶·6¹⁰⁵·8¹²)拓扑类型。更多还原

【Abstract】 In recent years,many coordination polymers or metal-organic frameworks have been synthesiszed,providing a variety of properties such as storage,exchange, catalysis,magnetic and optical properties.The organic ligands containing two or more carboxylate groups offer great potentials for fine control over coordination architectures.Under the guidance of crystal engineering,rigid aromatic phenylenediacrylic acid or phenylenetriacrylic acid are used as bridging ligands between metal ions,in combination with the use of chelate/pyridyl reagents as terminal ligands or bridging ligands.Twenty-six new coordination polymers, including one dimensional,two dimensional,and three dimensional motifs,have been prepared,and the magnetic and thermostability of some of the complexes have been characterized.This dissertation covers the following five parts:（1） Magnetic study of the coordination polymers based on different phenylenediacrylic acids:（ⅰ） We have revealed five layered compounds synthesized by the reaction of p-phenylenediacrylate or m-phenylenediacrylate acid（H₂ppda or H₂mpda） and transitional metal ions of Mn（Ⅱ）,Fe（Ⅱ） and Co（Ⅱ）. In all these compounds,the 2D rhombic layers feature single carboxylate bridges in the syn-anti mode and relatively inclined metal polyhedrons alternating along the bridges.Variable-temperature magnetic susceptibility measurements indicate the presence of antiferromagnetic in the M（Ⅱ）-carboxylate sheet,while compounds 1 and 2 exhibit spin-canted antiferromagnetism,with weak ferromagnetic transition at 3.8 K and 4k respectively.It is worth to note that compound 2 represents the first Fe（Ⅱ） compound containing the single-carboxylate bridged layers.（ⅱ） A novel 3D lanthanide coordination polymer with an unprecedented 3,7-connected topology （4,6²）₂（4²,6）(4⁷,6⁴,8¹⁰)was synthesized by a solvothermal technique from Nd（Ⅲ） ion and H₂mpda and structurally characterized.The magnetic properties is typical of the Nd（Ⅲ） ⁴I_9/2 ground state perturbed by the ligand field and probable antiferromagnetic exchange through tripleμ₂-oxygen bridges.（2） Syntheses,structures,and properties of Zinc（Ⅱ） and Cadmium（Ⅱ） coordination polymers with different phenylenediacrylic acids:Self-assembly of different ligands of H₂ppda and H₂mpda with Zn（Ⅱ） and Cd（Ⅱ） under different reaction conditions yielded six novle complexes varying from zero- to three-dimensions, showing that the reaction conditions and the configuration of ligands play crucial roles in controlling the topological structures of the supramolecular architectures.（3） Different phenylenediacrylic acids coordination polymers tuned by chelate terminal ligands:Six phenylenediacrylic acids metal-organic coordination polymers decorated chelating terminal ligands have been synthesized.X-ray analysis revealed that the structures consist of infinite 1D polymeric chains or 2D layers,and the packing modes of the frameworks were investigated.The framework stability and magnetic properties of some of the polymers also have been characterized.（4） Crystal engineering of coordination polymers with phenylenediacrylic acids and different bipyridyl bridging motifs:A series of novel 2D and 3D coordination compounds with entangled structures have been synthesized under hydrothermal conditions or diffusion method and structurally characterized by single crystal X-ray diffraction.The framework stability of some of the polymers has been investigated.（5） Syntheses and X-ray structures of manganese and cadmium coordination polymers based on new phenylenetriacrylic acid:The secondary building unit （SBU） has been identified as a useful tool in the constrution of metal-organic frameworks.We illustrate two new 3D coordination polymers based on the solvothermal reactions of H₃BTA with Mn（Ⅱ） or Cd（Ⅱ）.Syntheses,crystal structures,and structure analysis using the polymeric SBU approach are presented for each compound.The framework stability and magnetic properties of some of the polymers have been investigated.更多还原