【摘要】：磷光過渡金屬配合物因其優(yōu)良的光物理性質(zhì),引起了研究者的廣泛關(guān)注。基于銥、鉑、釕等的磷光過渡金屬配合物具有高的發(fā)光效率、易調(diào)節(jié)的激發(fā)波長和發(fā)射波長(覆蓋了整個(gè)可見光區(qū)域甚至近紅外)、大的斯托克斯位移(通常大于5000 cm-1)以及較長的發(fā)光壽命等特點(diǎn)。大的斯托克斯位移使其容易區(qū)分激發(fā)和發(fā)射從而減少自吸收過程,而較長的發(fā)射壽命(通常為幾百納秒到幾十微秒)使其能夠利用時(shí)間分辨技術(shù)來消除背景熒光的干擾。以上這些性質(zhì)使磷光過渡金屬配合物非常適合用于生物或化學(xué)傳感材料,在本論文中,我們旨在發(fā)展新的磷光過渡金屬配合物材料并研究其光物理性質(zhì)及對(duì)目標(biāo)分析物的響應(yīng)性。我們?cè)O(shè)計(jì)合成了3種具有聚集誘導(dǎo)發(fā)光增強(qiáng)效應(yīng)的鉑配合物,并實(shí)現(xiàn)了在活細(xì)胞成像中的應(yīng)用;此外,我們進(jìn)一步設(shè)計(jì)合成了一種猝滅型的次氯酸根磷光探針,實(shí)現(xiàn)了對(duì)次氯酸根離子的磷光檢測。主要研究內(nèi)容如下:1、聚集誘導(dǎo)磷光發(fā)射鉑配合物的設(shè)計(jì)、合成、光物理性質(zhì)及在細(xì)胞成像中的應(yīng)用在前期工作基礎(chǔ)上,我們進(jìn)一步將給電子或吸電子取代基引入席夫堿配體中,合成了三種新型的席夫堿鉑配合物,利用1H NMR對(duì)其結(jié)構(gòu)進(jìn)行了表征,對(duì)配合物ppyPtN-Ph F5的單晶結(jié)構(gòu)做了X-射線分析,并對(duì)其光物理性質(zhì)進(jìn)行了研究。室溫下,這三種配合物在溶液中是不發(fā)光的,在固體狀態(tài)下卻表現(xiàn)出很強(qiáng)的磷光發(fā)射,最大量子效率達(dá)到0.39。其中給電子甲氧基的引入對(duì)最大發(fā)射峰的位移影響不大,而吸電子取代基五氟苯基的引入使配合物的發(fā)射紅移。此外,我們利用具有核殼結(jié)構(gòu)的介孔二氧化硅納米粒子作為探針載體,將ppyPtN-Ph M吸附到介孔二氧化硅納米硅球中,形成納米磷光生物探針Pt1@MSN。納米磷光生物探針Pt1@MSN具有較低的生物毒性可以實(shí)現(xiàn)對(duì)活細(xì)胞中胞漿的成像,具有較好的成像效果。2、含對(duì)氨基苯酚醚基團(tuán)的磷光銥配合物的合成及其對(duì)次氯酸根離子的響應(yīng)性我們將對(duì)氨基苯酚醚基團(tuán)引入到銥配合物的環(huán)金屬配體中,設(shè)計(jì)合成了一種新型的次氯酸根離子的磷光探針I(yè)r1。利用1H NMR和質(zhì)譜對(duì)其結(jié)構(gòu)進(jìn)行了表征,并對(duì)其光物理性質(zhì)進(jìn)行了研究,配合物Ir1最大發(fā)射峰位于521 nm,呈現(xiàn)黃綠光發(fā)射。隨次氯酸根離子的加入,配合物Ir1中的對(duì)氨基苯酚醚基團(tuán)會(huì)以4-亞氨基環(huán)己烷-2,5-二烯酮脫去,配合物Ir1的磷光發(fā)射逐漸減弱,直至猝滅,實(shí)現(xiàn)了對(duì)次氯酸根離子的“Turn-off”型檢測。此外,配合物Ir1對(duì)次氯酸根離子具有較好的選擇性。
[Abstract]:Phosphorescent transition metal complexes have attracted much attention due to their excellent photophysical properties. Phosphorescence transition metal complexes based on iridium, platinum and ruthenium have high luminescence efficiency, easy to adjust excitation and emission wavelengths (covering the entire visible region and even near infrared). Large Stokes shift (usually more than 5000 cm-1) and longer luminescence lifetime. The large Stokes shift makes it easy to distinguish between excitation and emission, thus reducing the self-absorption process, while the longer emission lifetime (usually hundreds of nanoseconds to tens of microseconds) enables it to eliminate background fluorescence interference by using time-resolved techniques. These properties make phosphorescent transition metal complexes very suitable for use in biological or chemical sensing materials. We aim to develop new phosphorescent transition metal complex materials and study their photophysical properties and responsiveness to target analytes. We designed and synthesized three kinds of platinum complexes with aggregation induced luminescence enhancement effect and realized their applications in living cell imaging. In addition, we further designed and synthesized a quenched hypochlorite phosphorescence probe to detect hypochlorite ion. The main research contents are as follows: 1. The design, synthesis, photophysical properties and application in cell imaging of the aggregation induced phosphorescent platinum complex are based on the previous work. Three new Schiff base platinum complexes were synthesized by introducing electron donor or electron absorbent substituents into Schiff base ligands. Their structures were characterized by 1H NMR, and the single crystal structure of ppyPtN-Ph F5 was characterized by X-ray analysis. The photophysical properties are also studied. At room temperature, these complexes are not luminescent in solution, but exhibit strong phosphorescence emission in solid state. The maximum quantum efficiency is 0.39. The introduction of electron methoxy has little effect on the shift of the maximum emission peak, while the introduction of electron absorbing substituted pentafluorophenyl makes the emission red shift of the complex. In addition, we used mesoporous silica nanoparticles with core-shell structure as probe carrier to adsorb ppyPtN-Ph M onto mesoporous silica nanospheres to form nano-phosphorescence biological probe Pt1@MSN.. The nano-phosphorescence biological probe Pt1@MSN has low biotoxicity, which can realize the imaging of cytoplasm in living cells, and has a better imaging effect. Synthesis of Phosphoiridium complexes containing p-Aminophenol Ether Group and their responsiveness to hypochlorite Ions We introduced p-aminophenol ether groups into the cyclic metal ligands of iridium complexes. A novel phosphor probe Ir1. for hypochlorite ion was designed and synthesized. The structure and photophysical properties of the complex were characterized by 1H NMR and mass spectrometry. The maximum emission peak of the complex Ir1 was located at 521 nm,. With the addition of hypochlorite ion, the p-aminophenol ether group in the complex Ir1 was removed by 4-iminocyclohexane-2o 5-dienone, and the phosphorescence emission of the complex Ir1 decreased gradually until quenching. The determination of hypochlorite ion by "Turn-off" type was realized. In addition, the complex Ir1 has good selectivity for hypochlorite ion.
【學(xué)位授予單位】：南京郵電大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4;O657.3

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