【摘要】：由于金屬銥配合物具有較大的斯托克位移、量子產(chǎn)率高、壽命長(zhǎng),穩(wěn)定性強(qiáng),并且通過對(duì)配體的修飾和改變可以對(duì)其吸收光譜和發(fā)射光譜進(jìn)行調(diào)控。因此,金屬銥配合物被廣泛應(yīng)用到熒光探針,雙模式成像領(lǐng)域。考慮到銥的重原子效應(yīng)可以實(shí)現(xiàn)三線態(tài)氧到單線態(tài)氧的轉(zhuǎn)變,因此,金屬銥配合物在光動(dòng)力治療方面也引起了極大的關(guān)注。然而,絕大多數(shù)金屬銥配合物的吸收光譜目前還處于紫外可見光區(qū),并沒有達(dá)到診療所需要的600-900 nm的生物光區(qū),在很大程度上限制了金屬銥配合物在生物診療方面的應(yīng)用。具有高度共軛的電子體系的酞菁在近紅外可見光區(qū)具有強(qiáng)烈的吸收和特殊的熱化學(xué)穩(wěn)定性。尤其是,可以通過選擇金屬中心或外圍取代基調(diào)整他們的光物理和氧化還原性能。因此,已經(jīng)成為一類具有獨(dú)特電子和物理化學(xué)性質(zhì)的分子材料。利用金屬Ir(III)的重原子效應(yīng)和酞菁的近紅外吸收,酞菁銥配合物可望用于近紅外光熱、光動(dòng)力學(xué)治療。本論文設(shè)計(jì)合成了幾種具有近紅外吸收的金屬銥酞菁配合物,在吸收光譜的研究基礎(chǔ)上,探討了溶液中的光熱和單線態(tài)氧的產(chǎn)生等性質(zhì),具體內(nèi)容包括以下兩個(gè)方面:1.質(zhì)子化金屬銥酞菁配合物的合成、結(jié)構(gòu)及性質(zhì)研究通過引入給電子基團(tuán)增加meso-位的堿性,一步合成質(zhì)子化金屬銥酞菁配合物。晶體結(jié)構(gòu)表征進(jìn)一步確認(rèn)該質(zhì)子化金屬銥酞菁配合物具有完全平面的結(jié)構(gòu)。配合物在溶液中具有很好的光熱效果,其光熱轉(zhuǎn)化效率達(dá)到~24%,與鋅酞菁相比,銥酞菁配合物的光熱穩(wěn)定性明顯提高。以DPBF作為單線態(tài)氧指示劑,質(zhì)子化酞菁銥配合物在808 nm穩(wěn)態(tài)激光下具有較高的單線態(tài)氧產(chǎn)生能力。通過與鋅酞菁相比,該配合物具有更高的單線態(tài)氧產(chǎn)生效率。2.金屬銥酞菁配合物的合成、表征及光譜研究設(shè)計(jì)合成出兩種不同周環(huán)取代的金屬銥配合物,研究了不同共軛程度對(duì)金屬銥配合物的吸收光譜的影響;通過選用吡啶(Py)、N,N-二甲基四氨基吡啶(DMAP)等不同軸向配位能力的配體與質(zhì)子化金屬銥配合物進(jìn)行配位,得到三種不同金屬銥酞菁配合物,研究了具有不同給電子能力的軸向配體對(duì)金屬銥酞菁配合物的影響。
[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.
【學(xué)位授予單位】：上海師范大學(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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