质子化酞菁铱配合物的光谱调控研究

发布时间：2018-08-05 18:35

【摘要】：随着光电技术的兴起,酞菁在LB膜、光学存储介质、能量转换、光电导材料、半导体、电致变色、电致发光、非线性光学等诸多方面得到了广泛应用。本文设计合成了一种质子化酞菁铱配合物(IrPc HCl2),主要研究溶剂、浓度、酸及金属离子等因素对吸收光谱的调控,并对其机理进行初步探讨,具体内容包括以下三个方面:1.溶剂及浓度对IrPcHCl2的光谱调控设计合成了以酞菁为配体的铱配合物,通过核磁共振氢谱和高分辨率质谱表征了IrPcHCl2的结构,研究了在CH2Cl2,CHCl3,THF,DMSO,DMF,CH3CN等溶剂中的吸收光谱。结果表明,IrPcHCl2在CH2Cl2,CHCl3,THF中由于质子化作用使得酞菁环的对称性发生改变,从而导致其Q带分裂。IrPcHCl2在DMSO,DMF,CH3CN中呈现去质子化状态。并研究了在这六种溶剂中浓度对IrPcHCl2光谱的影响,在实验浓度范围内,IrPcHCl2并未发生明显的聚集。2.酸对IrPcHCl2的光谱调控在THF,CH2Cl2,苯甲腈中,分别研究了CF3SO3H和CF3CO2H对IrPcHCl2吸收光谱的调控。结果表明,酸的强度以及溶剂的极性会影响IrPcHCl2质子化程度,从而能引起吸收光谱的改变。3.银盐对IrPcHCl2的光谱调控围绕在两种溶剂中四种银盐(AgBF4,CF3SO3Ag,CH3COOAg,CF3COOAg)对IrPcHCl2的光谱调控。由于阴离子的碱性和配位能力的差异从而引起了吸收光谱的改变。但是,其他金属离子对其吸收光谱并不产生明显的影响,因此IrPcHCl2可以实现对银离子的高选择性比色检测。
[Abstract]:With the development of photoelectric technology, phthalocyanine has been widely used in LB films, optical storage media, energy conversion, photoconductive materials, semiconductors, electrochromic, electroluminescence, nonlinear optics and so on. In this paper, a proton iridium phthalocyanine complex (IrPc HCl2) was designed and synthesized. The absorption spectra were regulated by solvent, concentration, acid and metal ions, and its mechanism was preliminarily discussed, including the following three aspects: 1. The iridium complexes with phthalocyanine as ligand were designed and synthesized by the spectral regulation of solvent and concentration on IrPcHCl2. The structure of IrPcHCl2 was characterized by NMR and high resolution mass spectrometry. The results show that the symmetry of phthalocyanine ring changes due to the protonation of IrPcHCl2 in CH2Cl2CHCl3THF, which leads to the deprotonation of the Q-band splitting of IrPcHCl2 in DMSO-DMFU CH3CN. The influence of the concentration of the six solvents on the IrPcHCl2 spectra was also studied. The concentration of IrPcHCl2 did not show obvious aggregation in the range of experimental concentration. The spectral regulation of acid on IrPcHCl2 was studied in THF Ch _ 2Cl _ 2 and benzonitrile. The regulation of CF3SO3H and CF3CO2H on the absorption spectrum of IrPcHCl2 was studied. The results show that the intensity of the acid and the polarity of the solvent will affect the degree of IrPcHCl2 protonation, which can cause the change of absorption spectrum. The spectral regulation of silver salts on IrPcHCl2 is centered on the spectral regulation of IrPcHCl2 by four silver salts (AgBF4CF-3SO3AgCG-CH3COOAg). The absorption spectrum is changed due to the difference of anionic alkalinity and coordination ability. However, other metal ions have no obvious effect on the absorption spectra, so IrPcHCl2 can achieve high selectivity colorimetric detection of silver ions.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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