【作者】 冯丹；

【导师】 刘术侠；

【作者基本信息】 东北师范大学 ， 无机化学， 2010， 硕士

【摘要】 金属有机配位聚合物由于迷人的结构以及在催化、吸附、离子交换、非线性光学和荧光等方面的潜在应用而受到广泛的关注。尽管一些具有迷人体系和有趣性质的配位聚合物已被报道,但是在合成化学领域,寻找一个合理的策略来制备目标材料仍是一个巨大的挑战。考虑到一些因素对合成这类材料的影响,如金属离子、配体、溶剂和温度等,我们主要研究了刚性多齿配体(或混合配体)与金属锌离子反应来构筑新颖的配位聚合物。d10的球形构造和灵活的配位环境使锌配位聚合物的几何构型多样化,如四面体、三角双锥、四方锥、八面体以及一些扭曲的多面体构型。此外,由于锌的配位聚合物普遍存在的不稳定性,配位键的形成过程是可逆的,这就使金属离子和配体在聚合过程中发生重新排列,得到更高规则度的网络结构。锌离子可以构筑多种类型的体系结构,即使选择及其相似的配体,也极有可能得到完全不同的配位排列方式。通过溶剂热方法,我们合成了二个化合物,经元素分析、单晶X-射线衍射、XRPD、IR和TG分析对晶体结构进行了表征,并对化合物的荧光性质进行了初步讨论。化合物(H3O)2[Zn(BTEC)] (1)是一个包含一维菱形孔道的三维网络结构.孔道窗口最大尺寸为8?,最小为5 ?,一维菱形孔道沿着c轴方向无限延伸。[Zn2 (BDC) (4, 4′-bipy) (HCOO) 2] (2)是一个基于混合配体的化合物。它代表着第一例由三个混合配体(BDC, 4, 4′-联吡啶和甲酸配体)桥连的金属有机配位聚合物结构,在化合物2中,BDC, 4, 4′-联吡啶交替连接Zn(Ⅱ)中心形成一个锯齿形配位链,临近的锯齿链进一步通过甲酸配体连接得到一个无限拓展的二维屏风层结构。值得注意的是,作为桥连配体的甲酸来自于溶剂DMF的水解,它在反应中与锌离子配位,使化合物2结构得以稳定,这在配位化合物合成上是较少见到的。更多还原

【Abstract】 Metal-organic coordination polymers with well-regulated network structures has received considerable attention, mostly motivated by their intriguing structures and potential applications in the fields of catalysis, gas absorption, nonlinear optics, ion-exchange, luminescence and so on. Although a number of coordination polymers with intriguing architectures and interesting properties have been reported, a rational strategy to synthesize desired solid-state materials is still one of the great challenges in synthesis chemistry. Considering the synthetical factors on such materials, such as metal ion, ligand, solvent, temperature and so on, we investigated the reactions between the rigid multi-carboxylate ligands /mixed-ligand and Zn (Ⅱ) ions to construct novel coordination polymers. The spherical d10 configuration is associated with a flexible coordination environment so that geometries of Zn complexes can vary from tetrahedral through trigonal bipyramidal and square pyramidal to octahedral and severe distortion of the ideal polyhedron easily occurs. Furthermore, due to the general lability of Zn complexes the formation of coordination bonds is reversible which enables metal ions and ligands to rearrange during the process of polymerization to give highly ordered network structures. Consequently, Zn can readily accommodate all kind of architectures. In many cases rather similar ligands lead to completely different coordination arrays.Two compounds were isolated by solvothermal technique and structurally characterized by elemental analyses, XRPD, IR, single crystal X-ray diffractions and TG.. The luminescent properties were also investigated for the compounds.Compound (H3O)2[Zn(BTEC)] (1) is a three-dimensional network containing one-dimensional rhombic channels with the sizes of the windows are approximately 8 ? at the widest and 4.5 ? at the narrowest spacing (excluding the van der Waals radius of atoms in the framework) running along the c axis. [Zn2 (BDC) (4, 4′-bipy) (HCOO) 2] (2) is a compound based on mix-liangd. It provides the first coordination polymer structure constructed together by bridging BDC, 4, 4′-bipy and formate ligands. Both the BDC and 4, 4′-bipy link up zinc atoms alternatively resulting in a zigzag coordination chain, and adjacent chains are further linked by formates to form an infinite extended two-dimensional folding screen layer. Remarkably, the formate which comes from DMF hydrolyzation acting as bi-dentate bridging ligand coordinates to zinc ions, which has rarely been observed.更多还原