基于三芳胺的双自由基及多自由基化合物的研究

发布时间：2018-07-18 11:33

【摘要】：在自由基化学的研究当中,氮族自由基化学一直是研究的热点。众所周知,自由基具有较高的反应活性,易于发生聚合、夺氢、氧化、歧化等反应,因此大多数的自由基仅仅在溶液当中被检测到。由于这样的化学不稳定性,在自由基化学的研究当中,要解决的一个重要问题是如何稳定并且分离自由基化合物,并以此为基础,研究自由基在生物医学、电子学材料以及有机化学反应的应用。本篇论文总结了一系列含氮双阳离子以及含有多自由基化合物的研究现状,利用弱配位阴离子,稳定和表征了一系列双自由基以及三自由基化合物。并且结合量子化学计算对这些化合物的结构以及性质进行研究,为构建新型功能材料提供了设计思路。本论文的主要工作列举如下:一、以三芳胺的骨架为基础,分别得到中性化合物1-3,我们利用弱配位阴离子[A1(ORF)_4]~-(ORF = OC(CF_3)_3),成功地稳定了化合物 1~(2+)·2[A1(ORF)_4]~-和化合物1~(2+)·2[A1(ORF)_4]~-,并且分离得到了化合物3~(2+)·2[A1(ORF)_4]~-的晶体,对结构进行了 X-射线单晶衍射的研究。结合理论计算对1~(2+)、2~(2+)以及3~(2+)的几何构型以及电子组态进行了深入的研究。结果表明,1~(2+)、2~(2+)和3~(2+)的结构、各电子组态能量差、双自由基的性质、光学和磁学的性质可以通过中间桥联基团来调控。其中,1~(2+)和2~(2+)的基态为两个没有相互作用的独立的自由基,3~(2+)的基态为开壳层单线态,并且3~(2+)的三线态与单线态的能量差很小,很容易通过热激发使单线态转变为三线态。这种调控是通过中间桥联骨架的刚性来得以实现的。量化计算得到的电子自旋密度图显示,随着中间桥联基团的刚性增强,电子自旋密度的分布变得更加平均化,这样使得两个自由基的相互作用逐渐增强。该工作不仅得到了羰基桥联的双三芳胺双阳离子的自由基化合物,并且探索了新型稳定的双自由基体系,提供了一例稳定的单三线态能量差较小的双自由基化合物。二、合成了咔唑作为桥联基团连接两个三芳胺的化合物4-8以及二苯胺取代的1,3,5-苯基化合物9-11。利用弱配位阴离子[Al(ORF)_4]~-(ORF = OC(CF_3)_3),成功稳定得到了化合物 4~(2+)·2[Al(ORF)_4]~-,6~(2+)·2[Al(ORF)_4]~-,8~(2+)·2[A1(ORF)_4]~-和11~(2+)·2[Al(ORF)_4]~-的双自由基化合物以及6~(3+)·3[Al(ORF)_4]~-的三自由基化合物。通过实验表征手段以及量子化学计算对其结构以及性质进行了研究。结果表明,化合物 4~(2+)·2[Al(ORF)_4]~-,6~(2+)·2[Al(ORF)_4]~-和 8~(2+)·2[Al(ORF)_4]~-的基态为开壳层单线态。理论计算得到的化合物11~(2+)·2[Al(ORF)_4]~-的基态为开壳层三线态,这与之前报道的类似的化合物结果相一致。化合物11~(3+)·3[A1(ORF)_4]~-EPR测试结果显示出这个化合物是一个三自由基的化合物。该研究工作通过弱配位阴离子,得到了以三个氮为骨架的双自由化合物以及室温稳定的三自由的三阳离子。这些探索为进一步研究自由基在电学以及磁学方面的应用提供了新的设计思路。
[Abstract]:In the study of free radical chemistry, nitrogen free radical chemistry has always been a hot spot of research. It is known that free radicals have high reactive activity and are easy to react to polymerization, hydrogen capture, oxidation and disproportionation. Therefore, most of the free radicals are detected only in the solution. One of the important issues to be solved is how to stabilize and separate free radical compounds. On the basis of this, the application of free radicals in biomedicine, electronic materials and organic chemical reactions is studied. This paper summarizes the current research status of a series of nitrogen containing double yang ions and multi radical compounds, and uses weak coordination sites. Anions, stable and characterized a series of double free radicals and three radical compounds. The structure and properties of these compounds are studied by quantum chemical calculations, which provide a design idea for the construction of new functional materials. The main work of this paper is listed as follows: first, it is neutral on the basis of the skeleton of three aryl amines. Compound 1-3, we used the weak coordination anion [A1 (ORF) _4]~- (ORF = OC (CF_3) _3) to successfully stabilize the compound 1~ (2+) 2[A1 (ORF) _4]~- and compounds. The geometric configuration and electronic configuration of 2~ (2+) and 3~ (2+) have been studied in depth. The results show that the structure of 1~ (2+), 2~ (2+) and 3~ (2+), the energy difference of each electronic configuration, the properties of the double radicals, the properties of the optical and magnetic properties can be regulated by the intermediate bridge groups. Among them, the base state of 1~ (2+) and 3~ is independent of the interaction. The base state of 3~ (2+) is the open shell single state state, and the energy difference between the three line state of 3~ (2+) and the single line state is very small. It is easy to transform the single state state into the three wire state through the thermal excitation. This regulation is realized by the rigidity of the intermediate bridged skeleton. The electron spin density diagram obtained by quantitative calculation shows that with the intermediate bridging group As the mass of the mass is strengthened, the distribution of the electron spin density becomes more average, which makes the interaction of the two free radicals enhanced gradually. The work not only obtains the free radical compounds of the double three aromatic amine ion of the carbonyl bridge, but also explores a new stable double radical system, which provides a stable single three linear state energy. Two, two, the synthesis of carbazole as a bridging group connecting two three aryl amines 4-8 and the substituted 1,3,5- phenyl compound 9-11. using the weak coordination anion [Al (ORF) _4]~- (ORF = OC (CF_3) _3), successfully stabilized the compound 4~ (2+). The double radical compound of 2[A1 (ORF) _4]~- and 11~ (2+). 2[Al (ORF) _4]~- and the three free radical compounds of 6~ (3+). 3[Al (ORF). The structure and properties of the compounds were studied by means of experimental characterization and quantum chemical calculations. The base state of the open shell single state state. The base state of the compound 11~ (2+). 2[Al (ORF) _4]~- is the open shell three line state, which is in accordance with the similar compound results previously reported. The compound 11~ (3+). 3[A1 (ORF) _4]~-EPR test results show that the compound is a three radical compound. The coordination anion has obtained the double free compound with three nitrogen as the skeleton and the stable three free three sun ions at room temperature. These explorations provide a new design idea for the further study of the application of free radicals in the field of electricity and magnetism.
【学位授予单位】：南京大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O625.63

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