【摘要】：銥配合物由于具有高的發(fā)光效率、發(fā)光顏色可調(diào)、發(fā)光壽命長、大的Stokes位移、良好的光熱穩(wěn)定性等優(yōu)點(diǎn),使其在有機(jī)電致發(fā)光器件、電化學(xué)傳感器、細(xì)胞成像、熒光探針、光催化等領(lǐng)域引起了廣泛的關(guān)注。在金屬銥配合物的設(shè)計(jì)與合成中,一般利用環(huán)金屬配體作為主配體,用β-二酮、聯(lián)吡啶類配體作為輔助配體。通過主配體以及輔助配體的修飾,可以調(diào)節(jié)銥配合物的HOMO與LUMO的能級(jí)差,從而達(dá)到發(fā)光顏色可調(diào)的目的。配體的調(diào)節(jié)方式之一可以采用引入吸電子基團(tuán),比如氟原子,也可以引入供電子基團(tuán),比如甲基、乙基等。這些基團(tuán)可以引入到主配體中,也可以引入到輔助配體中。在本論文中,我們選用兩種不同的主配體,三類不同的輔助配體,合成了一系列具有良好發(fā)光性質(zhì)的銥配合物。利用氫核磁共振譜、紅外光譜對(duì)新配合物的組成進(jìn)行確定。配合物的結(jié)構(gòu)經(jīng)過單晶X-Ray衍射得到了進(jìn)一步確認(rèn)。通過熱重分析研究了配合物的熱穩(wěn)定性。利用紫外吸收光譜、熒光光譜研究了配合物的光物理性質(zhì)。利用理論量化計(jì)算研究了銥配合物的能級(jí)特點(diǎn)。本論文的研究內(nèi)容主要如下:以2-苯基吡啶(ppy)和2-(2,4-二氟苯基)吡啶(dfppy)為主配體,用含氟原子取代的β-二酮為輔助配體(六氟乙酰丙酮,三氟苯甲酰丙酮),合成了出了三元銥配合物A1、A2;通過對(duì)二苯甲酰甲烷的改性,分別引入供電子甲基和乙基,合成出了取代型β-二酮輔助配體。再利用該輔助配體,在主配體的存在下,合成出了三元銥配合物A3、A4、A5。利用有機(jī)羧酸作為輔助配體,成功制備出了兩種三元銥配合物A6、A7中性銥配合物。晶體結(jié)構(gòu)顯示,銥原子以六配位的方式形成變形的八面體結(jié)構(gòu),主配體提供四個(gè)配位原子,輔助配體提供兩個(gè)配位原子。光譜分析表明,通過改變輔助配體,能夠在一定程度上調(diào)節(jié)銥配合物的發(fā)光波長。同時(shí),金屬配合物的熱穩(wěn)定性也受到輔助配體的影響。
[Abstract]:Iridium complexes have many advantages such as high luminescence efficiency, tunable luminescence color, long luminescence lifetime, large Stokes shift, good photothermal stability, etc., which make iridium complexes in organic electroluminescent devices, electrochemical sensors, cell imaging, fluorescent probes, etc. Photocatalysis and other fields have attracted wide attention. In the design and synthesis of iridium complexes, cyclic metal ligands are generally used as main ligands, 尾 -diketones and bipyridine ligands as auxiliary ligands. By modifying the main ligands and auxiliary ligands, the energy difference between HOMO and LUMO of iridium complexes can be adjusted, so that the color of iridium complexes can be adjusted. One of the ways to regulate ligands is to introduce electron-absorbing groups, such as fluorine atoms, or donor groups, such as methyl, ethyl, etc. These groups can be introduced into the main ligands or into the auxiliary ligands. In this thesis, we have synthesized a series of iridium complexes with good luminescence properties by using two different principal ligands and three kinds of auxiliary ligands. The composition of the new complex was determined by nuclear magnetic resonance spectroscopy (NMR) and infrared spectroscopy (IR). The structure of the complex was further confirmed by single crystal X-Ray diffraction. The thermal stability of the complex was studied by thermogravimetric analysis. The photophysical properties of the complexes were studied by UV and fluorescence spectra. The energy level characteristics of iridium complexes have been studied by theoretical quantification calculation. The main contents of this thesis are as follows: the ligands of 2-phenylpyridine (ppy) and 2- (2- (2-) 4-difluorophenyl) pyridine (dfppy) were used as auxiliary ligands (hexafluoroacetone) with fluorine-containing atoms substituted 尾 -diketones. Trifluorobenzoyl acetone), a ternary iridium complex A1- (A2) was synthesized. The substituted 尾 -diketone auxiliary ligands were synthesized by the modification of p-dibenzoylmethane and the introduction of electron donor methyl and ethyl, respectively. In the presence of the principal ligand, the ternary iridium complex A _ 3O _ 4A _ 5 was synthesized by using the auxiliary ligand. Two ternary iridium complexes A _ 6 and A _ 7 neutral iridium complexes were successfully prepared by using organic carboxylic acids as auxiliary ligands. The crystal structure shows that the iridium atom forms a deformed octahedron structure in a hexagonal manner, the principal ligand provides four coordination atoms and the auxiliary ligand provides two coordination atoms. Spectral analysis shows that the luminescence wavelength of iridium complexes can be adjusted to some extent by changing the auxiliary ligands. At the same time, the thermal stability of the metal complexes is also affected by the auxiliary ligands.
【學(xué)位授予單位】：云南師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4

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