【作者】 牛琼；

【导师】 牛和林；

【作者基本信息】 安徽大学 ， 无机化学， 2012， 硕士

【摘要】 近年来,兴起的配位聚合物晶体材料因具有新颖的、迷人的拓扑结构以及在气体吸附和存储、分子磁体等新材料领域存在潜在的应用价值,因此对配合物的设计、合成已成为结构化学和材料化学领域的一个研究热点。控制目标产物结构是一个巨大挑战,因为自组装过程受各种因素的影响如配体结构、阴离子、温度和pH等。在这些因素中,其中配体结构在很大程度上决定配位聚合物最终结构,因此对配体的设计和选择至关重要。一般来说,羧酸类配体因具有多种配位模式,常用来作为构筑单元。近年来,一些因具有—CH2—重复单元柔性的含氮桥联配体因可以灵活弯曲和旋转,能更好的满足金属离子的配位数,被越来越多的配位聚合物研究者所使用。使用长配体得到的配位聚合物形成较大的孔洞可能性比较大,在气体吸附性方面将具有一定的应用价值。本文以含氧的多羧酸和柔性含氮的1,4-双(咪唑-1-基)丁烷作为混合配体,与过渡金属离子Ni2+,在水热体系中通过配位得到了三个结构新颖的配位聚合物单晶。通过对这些单晶进行X—射线衍射测试,得出了它们的空间结构。元素分析、粉末X-射线衍射、红外光谱、热重分析对其晶体结构进行了进一步表征且对部分晶体性质进行了研究。论文主要内容如下：1.160℃条件下通过水热合成得到金属聚合物单晶二[Ni(L1)(bbim-4)(H20)]n (L1=对苯二乙酸阴离子,bbim-4=1,4-双(咪唑-1-基)丁烷)。结构分析表明此配合物是通过金属镍离子与两种桥联配体形成两种不同的一维链,链与链组合形成二维的面,面与面之间通过范德华力作用形成了三维结构。变温磁化率研究表明镍原子之间存在反铁磁作用。2.在160℃条件下通过水热合成得到金属聚合物单晶三[Ni(L2)(bbim-4)(H20)]n (L2=邻苯二甲酸阴离子,bbim-4=1.4-双(咪唑-1-基)丁烷)。结构分析表明此配合物是一个三维的具有三角形孔道的多孔配位聚合物,对N2、H2和CO2均具有一定的吸附性质。变温磁化率研究表明该配位聚合物具有典型的铁磁行为。3.在140℃条件下通过水热合成得到金属聚合物单晶一[Ni(L1)(bbim-4)(H20)]n(L3=反丁烯二酸阴离子,bbim-4=1,4-双(咪唑-1-基)丁烷)。结构分析表明,镍离子被1,4-双(咪唑-1-基)丁烷配体以双齿桥联模式连接成一维的链,链与链之间通过反丁烯二酸形成了二维的面,二维的面通过倾斜穿插形成了一个三维的多聚连锁结构。反丁烯二酸与水分子之间形成的氢键,使三维的配位聚合物的结构更加稳定更多还原

【Abstract】 In recent years, research of the design and synthesis of coordination polymers has become a hotspot in structural chemistry and materials chemistry, not only their novel and fascinating topologies, but also tremendous potential applications such as gas adsorption, storage and separation, molecule magnets.The controllable synthesis of coordination polymers is still a great challenge because there are many factors that play important roles in their self-assembling such as the chemical structures of the ligands, the anions, reaction temperature, pH value. Among these factors, it is well-known that structures of the ligands play crucial roles in the design and construction of desirable coordination polymer. Therefore, the design and selection of ligands is crucial. Generally speaking, carboxylic acid compounds with variety of coordination modes are selectively used as building units. In recent years, some N-donor bridging ligands with-CH2-alkyl spacers have been widely used by coordination polymer researchers. Because the flexible nature of spacers allows the ligands to bend and rotate when coordinating to metal centers so as to conform to the coordination geometries of metal ions. Furthermore, coordination polymers made from long bridging ligands can possible give rise to the formation of large voids, which have some value in terms of gas adsorption. In this work, some carboxylate acids with O atoms and flexible1,1’-(1,4-butanediyl)bis(imidazole) with N atoms as mixed ligands are selectively used as building units reacting with metal ions Ni2+, lastly three novel complexes have been obtained by hydrothermal reaction through metal-ligand coordination. We obtained Crystal structures by X-ray single crystal diffraction. And their structures have been charactered by elemental analysis, powder X-ray diffraction, IR spectrum, and thermogravimetric analysis. Our main work as follows:1. A novel complex [Ni(L1)(bbim-4)]n (L1=p-Phenylenediacetic acid anions, bbim-4=1,1’-(1,4-butanediyl)bis(imidazole) was synthesized by hydrothermal reaction under160℃. In complex, the L2link the Ni (Ⅱ) ions to form a infinite 1D zigzag chain, which are further linked by L2in two bidentate chelating coordination fashion to give the2D layer structure. Lastly, the parallel2D networks stack along the along the c-axis to form a3D supramolecular structure via van der Waals interactions. Study of the variable-temperature magnetic susceptibility indicate there are antiferromagnetic between the NiⅡ ions.2. A novel complex [Ni(L2)(bbim-4)]n (L2=o-phthalate acid anion, bbim-4=1,1’-(1,4-butanediyl)bis(imidazole) was synthesized by hydrothermal reaction under160℃.Compound [Ni(bbim-4)(L1)]n is a three-dimensional porous coordination polymer with triangular channels. Gas adsorption and desorption toward N2, CO2, H2study suggest that the complex have adsorption properties. This nature of the χMT vs T curve is a signature of the global ferromagnetic behavior of the coordination polymer.3. A novel complex [Ni(L3)(bbim-4)(H2O)2]n (L3=fum anion, bbim-4=1,1’-(1,4-butanediyl)bis(imidazole) was synthesized by hydrothermal reaction under140℃. In the compound, the1,1’-(1,4-butanediyl)bis(imidazole) link the NiⅡ ions to form a infinite1D zigzag chain, which are further linked by fum anions to give the2D layer structure, then2D layers interpenetrated in an inclined mode to generate a unique3D polycatenation network. The hydrogen bonds exist between the water molecules and fum anions, which further stabilize the3D supramolecular structure.更多还原