含芳乙烯基的长链柔性二羧酸—联吡啶—金属超分子化合物的合成、结构与性能

发布时间：2018-03-13 19:21

本文选题：芳乙烯基　切入点：长链柔性二羧酸　出处：《重庆师范大学》2017年硕士论文　论文类型：学位论文

【摘要】：功能性金属-有机超分子聚合物得到了国内外科学家的高度重视,不仅因为其新颖的结构,而且在发光、催化、气体存储、分离等方面都具有潜在的应用价值。含芳乙烯基的柔性二羧酸或多羧酸因为多样的构象和配位模式,以及苯环π-π叠加、氢键等相互作用,有利于获得具有穿插、螺旋、缠绕等结构的功能超分子聚合物。然而,这类羧酸配体在超分子化学领域还没有得到深入开发。本论文用含芳乙烯基的长链柔性羧酸1,3-(2-丙烯酸基苯氧基)丙烷(H2ppa)作为O-配体。以不同联吡啶配体,1,2-bi(4-pyridyl)ethylene(简写为bpe),1,4-bis[2-(4-pyridyl)ethenyl]benzene(简写为bpeb),4,4'-bis[2-(4-pyridyl)ethenyl]biphenyl(简写为bpep),2,2-bipyridine(简写为2,2’-bpy)和4,4-bipyridine(简写为4,4’-bpy)作为N-配体。在溶剂热条件下,O-配体、N-配体分别与不同的d10过渡金属盐组装了八个新的超分子化合物,其组成分别为{[Zn4(bpe)3(ppa)4](H2O)6}n(1)、[Cd(ppa)(bpe)]n(2)、[Zn2(ppa)2(bpeb)]n(3)、[Co2(ppa)2(bpeb)](4)、[Zn2(ppa)2(bpep)]n(5)、[Zn(Hppa)2(2,2’-bpy)](H2O)(6)、[Zn2(ppa)2(4,4’-bpy)]n(7)和[Co2(ppa)2(4,4’-bpy)]n(8),其中化合物3与4、7与8分别为同构化合物。实验过程中,我们探究了溶液pH值、溶剂、温度、反应物配比等因素对超分子组装的影响。通过X-射线单晶衍射、红外、X-粉末衍射等手段对制备的超分子化合物进行表征和分析,测定化合物的热稳定性,研究了发光性能。X-射线单晶衍射揭示出,化合物1-5中存在着左右两种不同螺旋结构的一维链。化合物1,3,5是层状(2D)配位聚合物,并通过互锁形成了三维(3D)超分子结构。柔性配体ppa2-在这些化合物中呈现出不同的构型和不同的配位方式。同时在化合物1和3的互锁区域,两种不同的左手螺旋和右手螺旋结构交替排列。化合物5中,存在18.98?×16.27?维度纳米尺寸的环,相邻的二维层,进一步的互锁形成三维(3D)超分子结构。在化合物1,3,5中,O-配体ppa存在着不同的配位模式和构象。化合物2中,螺旋子通过共享金属离子形成了左手螺旋和右手螺旋结构(其交替排列在层状结构的两侧),并通过含氮配体进一步构筑了三维的配位超分子结构。化合物6是类似英文字母“W”的零维结构,进一步通过氢键构筑的二维网状超分子化合物,而化合物7也是含螺旋结构的柱撑的三维配位超分子化合物。论文研究了新超分子化合物的荧光性能,并探讨了荧光性质与相应电子结构之间的关系。上述的结构和性质,揭示了长链柔性羧酸,有利于组装螺旋、互锁等结构的超分子化合物,共轭的芳乙烯基的有利于得长波光敏性能。
[Abstract]:Functional metal-organic supramolecular polymers have attracted great attention from scientists at home and abroad, not only because of their novel structure, but also because of their luminescence, catalysis and gas storage. The flexible dicarboxylic acid or polycarboxylic acid containing aryl vinyl group is advantageous to the intercalation and helix because of its various conformation and coordination modes, as well as the interaction of benzene 蟺-蟺 superposition and hydrogen bond. Functional supramolecular polymers with structures such as winding. However, This kind of carboxylic acid ligands have not been further developed in the field of supramolecular chemistry. In this thesis, a long chain flexible carboxylic acid containing aryl vinyl group, 1 / 3-(2-(acrylic) phenoxy) propane (H _ 2ppa), was used as an Oligand. Different bipyridine ligands were used as Oligand with different bipyridine ligands: 1 / 2-bipyridylethylene. Benzene14-bis [2-Py 4-pyridylethenyl] benzene- bis [2-4-pyridylethenyl] biphenyl- (abbreviated as bpeptio 22-bipyridine (22-bpyine) and 44-bipyridine (44-bipyridine-4bpy4) as N-ligand. Eight new supramolecular compounds were assembled under solvothermal conditions, respectively, with different D10 transition metal salts. Their compositions are {[Zn4(bpe)3(ppa)4] H _ 2O _ 2 ~ (6)} n ~ (1), [CD _ (2) PPA ~ (2 +) ~ (2 +))] ~ (2) N ~ (2 +), [Zn _ (2) PPA _ (2) B _ (peb))] n ~ (7), [[Co _ (2) PPA _ (2) H _ 2O _ (2) B _ (peb))] _ (4), [[Co _ (2) PPA _ (2) H _ 2O _ (2) B _ (P))] ~ (2) ~ (1), [[Zn _ (2) Zn4(bpe)3(ppa)4] ~ (2) H _ 2O _ (2) B _ (p) ~ (2) H _ 2O _ (2) H _ 2O _ (2) H _ (2) H _ (2) H _ (2) H _ (2) O _ (2) H _ (2) O _ (1), [[Zn _ (2) PPA _ (2) PPA _ (2) O _ (2) B _ (PY))]? The effect of reactant ratio on supramolecular assembly. The supermolecular compounds were characterized and analyzed by means of X-ray single crystal diffraction and infrared X-ray powder diffraction to determine the thermal stability of the compounds. The photoluminescence properties. X- ray single crystal diffraction revealed that there are two different helical chains in compound 1-5. Compound 1: 3 (5) is a lamellar 2D) coordination polymer. The flexible ligand ppa2- presents different configurations and different coordination modes in these compounds. At the same time, the interlocking regions of compounds 1 and 3 are found. Two different spiral structures of left hand and right hand are arranged alternately. In compound 5, 18.98? 脳 16.27? Dimensional nanoscale rings, adjacent two-dimensional layers, and further interlocking to form a three-dimensional (3D) supramolecular structure. In compound 1, 3, 5, there are different coordination modes and conformations for the ligand ppa. In compound 2, Helicons form left-handed and right-hand spiral structures by sharing metal ions, which alternately arrange on both sides of the layered structure, and further construct a three-dimensional coordination supramolecular structure through nitrogen-containing ligands. Compound 6 is analogous. The zero-dimensional structure of the English letter "W", Furthermore, 2-D network supramolecular compounds were constructed by hydrogen bonding, and compound 7 was also a three-dimensional coordination supramolecular compound with helical structure. The fluorescence properties of new supramolecular compounds were studied in this paper. The relationship between the fluorescence properties and the corresponding electronic structures is discussed. The structure and properties above reveal that long chain flexible carboxylic acids are conducive to the assembly of supramolecular compounds with helical and interlocking structures. The conjugated aryl vinyl group is advantageous to the long wave Guang Min performance.
【学位授予单位】：重庆师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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