本文選題：三亞苯 + PDAH_2��； 參考：《西北大學(xué)》2016年碩士論文

【摘要】：由于多結(jié)合位點(diǎn)的配體在催化領(lǐng)域和材料科學(xué)領(lǐng)域有著更多的潛在優(yōu)勢(shì),近幾年這類配體引起了人們的廣泛關(guān)注。在本文中,三亞苯作為一種典型的平面剛性大共軛分子能夠作為多齒配體的基本骨架。鄰苯二胺類衍生物(ortho-Phenylene diamines,縮寫：PDAH_2)是典型的含氮雙齒配體,其易修飾可以作為優(yōu)良的新型配體前驅(qū)體。在我們先前對(duì)兩例空間位阻較大含氮配體α-二亞胺和2,5-二胺基-1,4-苯醌二亞胺配體(取代基為2,6-二異丙基苯基)及配合物研究的基礎(chǔ)上,以三亞苯和鄰苯二胺為基礎(chǔ)骨架設(shè)計(jì)合成了三亞苯基六胺配體LH_6,并與堿金屬鈉,鉀和正丁基鋰試劑合成了四例堿金屬化合物[(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).通過(guò)核磁共振(NMR)、X-射線單晶衍射、IR. UV-VIS、CV、DFT理論計(jì)算等一系列方法對(duì)三亞苯基配體LH_6和化合物1-4的晶體結(jié)構(gòu)和光學(xué)性質(zhì)進(jìn)行了深入研究。全文共分為三部分：一.介紹了鄰苯二胺類衍生物的氧化還原活性和配位方式,總結(jié)了α-二亞胺和鄰苯二胺配體及苯醌二亞胺配體的合成方法,配位方式及具有代表性的金屬有機(jī)化合物,歸納了以三亞苯為骨架的新型配體的發(fā)展現(xiàn)狀；二.闡述了以三亞苯和鄰苯二胺為骨架設(shè)計(jì)合成了三亞苯基六胺配體LH_6,并通過(guò)核磁共振(NMR)、X-射線單晶衍射、循環(huán)伏安等測(cè)試手段對(duì)其進(jìn)行了表征；三.研究了有關(guān)配體LH_6與不同當(dāng)量的堿金屬鈉,鉀及正丁基鋰試劑反應(yīng)得到的四例堿金屬化合物1-4,由晶體結(jié)構(gòu)可知,配合物隨著堿金屬離子半徑的不斷增大而呈現(xiàn)不同的配位形式。結(jié)合理論計(jì)算模擬,化合物1-4的紫外可見光譜中中低能量處的吸收帶可歸屬為配體到金屬(LMCT)的電子躍遷。
[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, 偽 -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 偽 -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.
【學(xué)位授予單位】：西北大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O641.4

【相似文獻(xiàn)】

相關(guān)期刊論文 前10條

1 錢世準(zhǔn);;從水泥窯灰中制取鉀肥的方法[J];建材工業(yè)信息;1988年03期

2 村上高^(guò)，

本文編號(hào)：1980962