有机酸、二茂铁类配合物的合成、结构及性能研究

【作者】 李金鹏；

【导师】 候红卫；

【作者基本信息】 郑州大学 ， 无机化学， 2003， 硕士

【摘要】 本文报道了一种二茂铁配体的制备方法，以及两个Co（Ⅱ），Pb（Ⅱ）的配位聚合物和三个Ag（Ⅰ）、Cd（Ⅱ）的超分子化合物的合成、表征，培养得到了两个配位聚合物和三个超分子化合物的单晶，并采用RAXIS-Ⅳ面探仪对它们的晶体结构进行了测定，同时进一步研究了部分化合物的热性能。 合成并测定了晶体结构的配位聚合物有： {[Pb（H₂O）（C₈H₄O₄）]（DMF）}_n（1）。在这个聚合物中，多个Pb（Ⅱ）通过对苯二羧酸根配体的桥联作用，形成了一个一维的无限延展的锯齿状长链。相邻的长链又通过链间的氢键连接，进一步构成了一个三维的网状固态结构。差热及热重的测试结果表明，该聚合物在168℃-510℃温度范围内，逐步分解。 {Na₆Co（SO₄）₄（H₂O）₂}_n（2）。它是一个通过SO₄^2-桥联多个Co（Ⅱ）以及Na（Ⅰ）离子所形成的一个结构独特的三维网状聚合物。中心Co原子为六配位，均为氧配位。其中有四个氧来自于四个SO₄^2-离子，另两个氧来自于配位水。钠离子有三种配位形式，一种为八配位，两种为六配位。 合成并测定了晶体结构的有机超分子化合物有： {（AgI₃）（4-HBPFA）₂（H₂O）}（3）该超分子化合物是以[AgI₃]^2-为中心，通过氢键同二茂铁配体相连。同时，二茂铁配体的取代基通过氢键同另一分子[AgI₃]^2-相连，从而连接成一种类似于灯笼状的三维网状超分子结构。 {Cd(FeC₁₈H₁₇O₆)₂（H₂O）₄}（4）。该超分子化合物也具有三维的网状结构。中心原子Cd为六配位，均为氧配位，这六个氧来自于两分子配体上的两个单齿氧和四个配位水中的四个氧。该超分子化合物中的氢键主要由配位水上的OH基团与配体分子上的螯合氧和单齿氧作用而形成，这些氢键的作用下形成了三维的网状固态结构。差热及热重的测试结果表明：该超分子化合物从192℃起开始分解，到420℃分解完成。 [Cd（C₆H₄O₂N）₂（H₂O）₄]（5）。该超分子化合物同样具有三维网状结构。中心原子Cd为六配位，均为氧配位。分子间的氢键主要由配位水上的OH与配体分子的两端没有参郑州大学2003届硕士毕业论文与配位的单齿氧所形成，这些氢键的连接形成了具有三维网状结构的化合物。差热及热重的测试结果表明，该超分子化合物在137弋至44以C温度范围内，梯次分解。更多还原

【Abstract】 One ferrocenyl-based ligand, two coordination polymers of Co(II), Pb(II) and three supramolecular complexes of Ag(I), Cd(II) were prepared, and characterized by elemental analysis and IR spectrum. Furthermore, The crystal structures of coordination polymers Co(II), Pb(II) and supramolecular complexes Ag(I), Cd(II) were determined by single crystal diffraction analysis.Polymer {[Pb(H2O)(C8H4O4)](DMF)}n (1) shows 1-D zigzag linear structure, in which central Pb(II) ion is a tetrahedral environment and coordinate with oxygen atoms from two organic ligands and one H2O. Neighboring [Pb(C4H4O8)(H2O)]n chains were bridged byO-H-O hydrogen bonds leading to a 3-D network solid-state structure. The TGA study of the polymer indicates that it underwent a two-step decomposition process from 168℃ to 510℃.Polymer {Na6Co(SO4)(H2O)2}n (2) shows 3-D network structure, in which contain hollow vacuous cavity . All Co atoms are coordinated by six oxygen atoms, which come from four SO42- ions and two H2O molecules. All Na atoms are coordinated by six oxygen atoms or eight oxygen atoms, which come from SO42- ions and H2O moleculars.Supramolecular compound [(Agl3)(H2O)(4-HBPFA)2] (3) shows 3-D network structure, which looks like many lanterns hung on the trees. [(Agl3)(H2O)(4-HBPFA)2] shows3-D network structure, (4-HBPFA) connects with [AgI3]2- by I-H-O, I--H-N and I-H-C hydrogen bonds and leads to a 3-D supramolecular compound.Supramolecular compound {Cd(FeC|gHi7O6)2(H2O)4} (4) has a 3-D irregular network structure. Cd atom is coordinated by six oxygen atoms, which come from two organic ligands and four H2O molecules. [Cd(FeC18H17O6)2(H2O)4] connects with [Cd(FeC18H177O6)2(H2O)4] byO-H-O hydrogen bonds and leads to a 3-D network structure .The result of TGA study to supramolecular compound 4 shows that it underwent two-step decomposition processes from 192癈to384癈Supramolecular compound {Cd(C6H4O2N)2(H2O)4} (5) has a 3-D network structure, in which Cd atom is coordinated with six oxygen atoms which come from two organic ligands andfour H2O molecules, [Cd(C6O2N)(H2O4)] connects with [Cd(C6H4O2N)2(H2O)4] by O-H-O hydrogen bonds and lead a 3-D supramolecular compound. TGA studies indicate that the compound has a two-step decomposition process from 134癈 to 440癈The two ferrocenyl organic ligands are as follows:更多还原