具有近红外吸收的金属铱配合物的合成与性质研究

发布时间：2018-11-12 09:49

【摘要】：由于金属铱配合物具有较大的斯托克位移、量子产率高、寿命长,稳定性强,并且通过对配体的修饰和改变可以对其吸收光谱和发射光谱进行调控。因此,金属铱配合物被广泛应用到荧光探针,双模式成像领域。考虑到铱的重原子效应可以实现三线态氧到单线态氧的转变,因此,金属铱配合物在光动力治疗方面也引起了极大的关注。然而,绝大多数金属铱配合物的吸收光谱目前还处于紫外可见光区,并没有达到诊疗所需要的600-900 nm的生物光区,在很大程度上限制了金属铱配合物在生物诊疗方面的应用。具有高度共轭的电子体系的酞菁在近红外可见光区具有强烈的吸收和特殊的热化学稳定性。尤其是,可以通过选择金属中心或外围取代基调整他们的光物理和氧化还原性能。因此,已经成为一类具有独特电子和物理化学性质的分子材料。利用金属Ir(III)的重原子效应和酞菁的近红外吸收,酞菁铱配合物可望用于近红外光热、光动力学治疗。本论文设计合成了几种具有近红外吸收的金属铱酞菁配合物,在吸收光谱的研究基础上,探讨了溶液中的光热和单线态氧的产生等性质,具体内容包括以下两个方面:1.质子化金属铱酞菁配合物的合成、结构及性质研究通过引入给电子基团增加meso-位的碱性,一步合成质子化金属铱酞菁配合物。晶体结构表征进一步确认该质子化金属铱酞菁配合物具有完全平面的结构。配合物在溶液中具有很好的光热效果,其光热转化效率达到~24%,与锌酞菁相比,铱酞菁配合物的光热稳定性明显提高。以DPBF作为单线态氧指示剂,质子化酞菁铱配合物在808 nm稳态激光下具有较高的单线态氧产生能力。通过与锌酞菁相比,该配合物具有更高的单线态氧产生效率。2.金属铱酞菁配合物的合成、表征及光谱研究设计合成出两种不同周环取代的金属铱配合物,研究了不同共轭程度对金属铱配合物的吸收光谱的影响;通过选用吡啶(Py)、N,N-二甲基四氨基吡啶(DMAP)等不同轴向配位能力的配体与质子化金属铱配合物进行配位,得到三种不同金属铱酞菁配合物,研究了具有不同给电子能力的轴向配体对金属铱酞菁配合物的影响。
[Abstract]:Because of the large Stoke shift, high quantum yield, long lifetime and strong stability, the iridium complexes can adjust their absorption and emission spectra by modifying and changing their ligands. Therefore, the metal iridium complexes have been widely used in the field of fluorescence probe and double mode imaging. Considering that the heavy atom effect of iridium can realize the transition from three-wire oxygen to singlet oxygen, the iridium complexes have attracted much attention in photodynamic therapy. However, the absorption spectra of most of the iridium complexes are still in the ultraviolet and visible region, which does not reach the 600-900 nm bioluminescence region, which limits the application of iridium complexes in biological diagnosis and treatment to a great extent. Phthalocyanines with highly conjugated electron systems have strong absorption and special thermochemical stability in the near infrared visible region. In particular, their photophysical and redox properties can be adjusted by selecting metal centers or peripheral substituents. Therefore, it has become a class of molecular materials with unique electronic and physicochemical properties. Based on the heavy atom effect of metal Ir (III) and the near infrared absorption of phthalocyanine, iridium phthalocyanine complexes are expected to be used for photothermal and photodynamic therapy. In this paper, several metal iridium phthalocyanine complexes with near infrared absorption have been designed and synthesized. Based on the study of absorption spectra, the properties of photoheat and singlet oxygen generation in solution have been discussed. The specific contents include the following two aspects: 1. Synthesis, structure and Properties of Iridium phthalocyanine complexes with protonated Metals; Iridium phthalocyanine complexes were synthesized by introducing electron groups to increase the alkalinity of meso- sites. The crystal structure characterization further confirmed that the protonated iridium phthalocyanine complex has a complete planar structure. The iridium phthalocyanine complex has a good photothermal effect in solution, and its photothermal conversion efficiency reaches ~ 24%. Compared with zinc phthalocyanine, the photothermal stability of iridium phthalocyanine complex is obviously improved. Using DPBF as a singlet oxygen indicator, the protonated iridium phthalocyanine complex has a high singlet oxygen production ability under 808 nm steady state laser. Compared with zinc phthalocyanine, the complex has higher singlet oxygen production efficiency. 2. 2. Synthesis, characterization and Spectral study of Iridium phthalocyanine complexes. Two kinds of metal iridium complexes with different ring substitutions were designed and synthesized. The effects of conjugation degree on the absorption spectra of iridium complexes were studied. Three kinds of metal iridium phthalocyanine complexes were obtained by ligand coordination with protonated iridium complexes with pyridine (Py), N-dimethyl tetraaminopyridine (DMAP) and other ligands with different axial coordination abilities. The effects of axial ligands with different electron donor capacities on the iridium phthalocyanine complexes were investigated.
【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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