几种发光铱配合物的合成、表征及其晶体结构

发布时间：2018-11-01 19:27

【摘要】：铱配合物由于具有高的发光效率、发光颜色可调、发光寿命长、大的Stokes位移、良好的光热稳定性等优点,使其在有机电致发光器件、电化学传感器、细胞成像、荧光探针、光催化等领域引起了广泛的关注。在金属铱配合物的设计与合成中,一般利用环金属配体作为主配体,用β-二酮、联吡啶类配体作为辅助配体。通过主配体以及辅助配体的修饰,可以调节铱配合物的HOMO与LUMO的能级差,从而达到发光颜色可调的目的。配体的调节方式之一可以采用引入吸电子基团,比如氟原子,也可以引入供电子基团,比如甲基、乙基等。这些基团可以引入到主配体中,也可以引入到辅助配体中。在本论文中,我们选用两种不同的主配体,三类不同的辅助配体,合成了一系列具有良好发光性质的铱配合物。利用氢核磁共振谱、红外光谱对新配合物的组成进行确定。配合物的结构经过单晶X-Ray衍射得到了进一步确认。通过热重分析研究了配合物的热稳定性。利用紫外吸收光谱、荧光光谱研究了配合物的光物理性质。利用理论量化计算研究了铱配合物的能级特点。本论文的研究内容主要如下:以2-苯基吡啶(ppy)和2-(2,4-二氟苯基)吡啶(dfppy)为主配体,用含氟原子取代的β-二酮为辅助配体(六氟乙酰丙酮,三氟苯甲酰丙酮),合成了出了三元铱配合物A1、A2;通过对二苯甲酰甲烷的改性,分别引入供电子甲基和乙基,合成出了取代型β-二酮辅助配体。再利用该辅助配体,在主配体的存在下,合成出了三元铱配合物A3、A4、A5。利用有机羧酸作为辅助配体,成功制备出了两种三元铱配合物A6、A7中性铱配合物。晶体结构显示,铱原子以六配位的方式形成变形的八面体结构,主配体提供四个配位原子,辅助配体提供两个配位原子。光谱分析表明,通过改变辅助配体,能够在一定程度上调节铱配合物的发光波长。同时,金属配合物的热稳定性也受到辅助配体的影响。
[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.
【学位授予单位】：云南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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