金属锇杂呋喃与腈基配体的取代反应及气致变色研究

发布时间：2018-11-24 14:08

【摘要】：金属杂芳香化合物是传统的杂芳香化合物的一个碳氢基团被过渡金属及其配体取代而得到的一类d-pπ共轭体系。由于金属杂芳香化合物可能具有光、电、磁或催化性能,而日益引起人们的关注。目前主要是金属杂环芳香化合物的合成和反应性研究,但对于其在超分子自组装方向的研究较少,且存在不稳定,合成困难等缺点,大多数金属杂环芳香化合物的性质研究尚处于起步阶段,我们希望通过研究金属锇杂呋喃与双齿的柔性配体合成超分子环状化合物的反应,探索这类化合物的光学性质。本课题组之前的工作中,锇杂呋喃化合物与腈类配体,如乙腈、苯乙腈、对苯二乙腈反应,可以取代与锇配位的两个Cl离子,得到一系列双腈配位的金属锇杂呋喃化合物。但对其性质尚未作进一步的研究,本论文首先合成了底物叔丁氧基锇杂呋喃2-3,再与苯乙腈、对苯二乙腈、联苯二乙腈发生配体取代反应,得到四种金属锇杂呋喃2-4,2-5,2-6,2-7,并用核磁、X-射线单晶衍射和高分辨质谱进行了表征。研究发现当使用双齿的柔性配体对苯二乙腈、联苯二乙腈与金属锇杂呋喃进行配位取代反应,易生成具有椅式结构的金属环状超分子化合物,与课题组之前合成的化合物3-1,3-2结构类似,这些具有椅式结构的化合物吸附有机挥发性溶剂,颜色会从黄色变为橙红色,通过研磨又能变回黄色,显示出稳定的气致变色现象。我们初步研究了气致变色机理,具有椅式构象的金属环状化合物吸附有机蒸气分子后易形成分子间作用力引起电子跃迁导致颜色发生了变化,且这些作用力在失去有机蒸气分子后依然存在。只有给予机械研磨才能破坏这种的作用力,使固体的颜色恢复。这种具有特殊结构的椅式构象的金属环状化合物的高稳定性的气致变色行为很少见。我们期望通过研究这些化合物的气致变色机理得到比较稳定、灵敏的气致变色材料,能应用于化学传感器,环境监测器等领域。
[Abstract]:Metal hetero-aromatic compounds are a kind of d-p 蟺 conjugate system which is obtained by substitution of a hydrocarbon group of traditional hetero-aromatic compounds by transition metals and their ligands. Metal hetero-aromatic compounds have attracted increasing attention due to their potential light, electrical, magnetic or catalytic properties. At present, the synthesis and reactivity of metal heterocyclic aromatic compounds are mainly studied. However, there are few studies on the direction of supramolecular self-assembly and some disadvantages, such as instability, difficulty in synthesis, etc. The study of the properties of most metal heterocyclic aromatic compounds is still in its infancy. We hope to explore the optical properties of these compounds by studying the synthesis of supramolecular ring compounds from osmium heterocyclic furans and didentate flexible ligands. In our previous work, osmium heterofuran compounds reacted with nitrile ligands, such as acetonitrile, phenylacetonitrile and p-phenyldiacetonitrile, which could replace two Cl ions coordinated with osmium. However, no further study has been done on its properties. In this paper, tert-butyl osmium heterofuran 2-3 was synthesized, and then ligand substitution reaction with phenylacetonitrile, p-phenyldiacetonitrile and biphenyl diacetonitrile was carried out. Four kinds of osmium heterofuran 2-4N 2-5N 2-6N 2-7 were obtained and characterized by NMR, X-ray single crystal diffraction and high resolution mass spectrometry. It was found that when benzodiacetonitrile, biphenyl diacetonitrile and osmium heterofuran were coordinated to replace benzodiacetonitrile and biphenyl diacetonitrile, metal cyclic supramolecular compounds with chair structure were easily formed. Similar to the structure of compounds 3-1C 3-2 synthesized before the task force, these compounds with chair structures adsorb volatile organic solvents, which change from yellow to orange-red, and can be ground back to yellow. It shows stable gas discoloration. We have preliminarily studied the mechanism of gas chromotropic reaction. The metal ring compounds with chair conformation are easy to form intermolecular force after adsorbing organic vapor molecules, which results in the change of color due to electron transition. And these forces still exist after the loss of organic vapor molecules. Only mechanical grinding can destroy this force and restore the color of the solid. The highly stable gas-chromotropic behavior of this metal ring compound with a special structure in chair conformation is rare. We hope that these compounds can be applied to chemical sensors, environmental monitors and so on.
【学位授予单位】：华中师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

【相似文献】