三亚苯基六胺配体及其多核碱金属化合物的合成与性质研究

发布时间：2018-06-05 06:22

本文选题：三亚苯 + PDAH_2　；参考：《西北大学》2016年硕士论文

【摘要】：由于多结合位点的配体在催化领域和材料科学领域有着更多的潜在优势,近几年这类配体引起了人们的广泛关注。在本文中,三亚苯作为一种典型的平面刚性大共轭分子能够作为多齿配体的基本骨架。邻苯二胺类衍生物(ortho-Phenylene diamines,缩写：PDAH_2)是典型的含氮双齿配体,其易修饰可以作为优良的新型配体前驱体。在我们先前对两例空间位阻较大含氮配体α-二亚胺和2,5-二胺基-1,4-苯醌二亚胺配体(取代基为2,6-二异丙基苯基)及配合物研究的基础上,以三亚苯和邻苯二胺为基础骨架设计合成了三亚苯基六胺配体LH_6,并与碱金属钠,钾和正丁基锂试剂合成了四例碱金属化合物[(LH_4)Na_2(DME)_5]0.5DME·0.75n-hexane (1), [(LH_4)K_2(DME)_4](2), [(LH_3)K_3 (DME)_6] (3)和[(L)Li_6(DME)_6]-DME·toluene (4).通过核磁共振(NMR)、X-射线单晶衍射、IR. UV-VIS、CV、DFT理论计算等一系列方法对三亚苯基配体LH_6和化合物1-4的晶体结构和光学性质进行了深入研究。全文共分为三部分：一.介绍了邻苯二胺类衍生物的氧化还原活性和配位方式,总结了α-二亚胺和邻苯二胺配体及苯醌二亚胺配体的合成方法,配位方式及具有代表性的金属有机化合物,归纳了以三亚苯为骨架的新型配体的发展现状；二.阐述了以三亚苯和邻苯二胺为骨架设计合成了三亚苯基六胺配体LH_6,并通过核磁共振(NMR)、X-射线单晶衍射、循环伏安等测试手段对其进行了表征；三.研究了有关配体LH_6与不同当量的碱金属钠,钾及正丁基锂试剂反应得到的四例碱金属化合物1-4,由晶体结构可知,配合物随着碱金属离子半径的不断增大而呈现不同的配位形式。结合理论计算模拟,化合物1-4的紫外可见光谱中中低能量处的吸收带可归属为配体到金属(LMCT)的电子跃迁。
[Abstract]:Due to the potential advantages of multi-binding ligands in the field of catalysis and material science, these ligands have attracted much attention in recent years. In this paper, triphenyl, as a typical planar rigid large conjugate molecule, can be used as the basic skeleton of polydentate ligands. Ortho-Phenylene diamines2 (abbreviated as: PDAH-2) is a typical nitrogen-containing didentate ligand, which can be easily modified as a new kind of excellent ligand precursor. On the basis of our previous studies on two nitrogen-containing ligands with large steric hindrance, 伪 -diimide and 2o 5-diamino-4-benzoquinone diimide ligands (the substituents are 2o 6-diisopropyl phenyl) and their complexes, Based on the framework of Sanya and o-phenylenediamine, four alkaline-metal compounds (LH4DME6), [LHH3K2DME4] 0.5DME 0.75n-hexane, [LHH3K3DME6] and [LH3K3DME6] and [LH3DME6] DMET were synthesized with alkaline-metal compounds [LH4H4nNa2DME5] 0.5DME 0.75n-hexane 1, [LHV4K2DME4], LH3DME6) and [LH3DME6] and [LH3K5 DME6] DME toluene. X-ray single crystal diffraction (IR) was obtained by NMR. The crystal structure and optical properties of triphenyl ligand LH_6 and compound 1-4 have been studied by a series of methods such as UV-VIS-CVDFT. The full text is divided into three parts: 1. The redox activity and coordination mode of o-phenylenediamine derivatives were introduced. The synthesis methods, coordination methods and representative organometallic compounds of 伪 -diimide, o-phenylenediamine ligands and benzoquinone diimide ligands were summarized. The development status of novel ligands with triphenyl as skeleton was summarized. In this paper, the ligand LH6 was designed and synthesized by using triphenyl and o-phenylenediamine as skeleton, and characterized by NMR-X ray single crystal diffraction and cyclic voltammetry. Four alkaline-metal compounds 1-4 obtained by the reaction of ligands LH_6 with different equivalent alkali sodium, potassium and Ding Ji lithium reagents were studied. The crystal structure shows that the complexes exhibit different coordination forms with the increasing radius of alkali metal ions. In combination with theoretical simulations, the absorption bands at the low energy level of the UV-Vis spectra of compound 1-4 can be attributed to the electronic transition from ligands to LMCTs.
【学位授予单位】：西北大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

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