新型离子型铱、钌配合物光电材料的制备及其传感性能的研究
发布时间：2018-09-19 20:00
【摘要】：过渡金属铱、钌配合物由于其中心金属的重原子效应增强了自旋-轨道耦合作用,使得单线态和三线态之间的系间窜越成为可能,从而同时得到单重激发态和三重激发态,最终导致铱、钌配合物具有室温磷光的特性。磷光铱、钌配合物由于其具有较高的发光量子效率、较长的发光寿命、大的斯托克斯位移和易调节的发光波长等优点受到人们广泛的关注,并且在有机发光二极管(OLEDs )、发光电化学池(LECs )、光动力疗法(PDT)、光学传感器和生物成像等领域有了一定的应用。本文通过化学键引入特殊官能团(识别基团)修饰配合物的第一或辅助配体得到新型铱、钌配合物,利用识别基团与被检测物配位或化学反应产生的独特光致发光变化来实现对铜离子、次氯酸根离子和半胱氨酸的磷光传感。本论文内容分为三个部分,第一部分是修饰离子捕获基团二甲基吡啶胺(DPA)的强磷光铱或钌配合物作为“Turn-Off"型磷光探针对二价铜离子传感的研究(包括第二章、第三章)。第二部分是含有共轭碳氮双键结构的弱发光铱配合物作为“Turn-On”型磷光传感器对次氯酸根离子光致发光传感研究(第四章)。第三部分是利用配体上的烯键与半胱氨酸的巯基之间的迈克尔加成来进行新型配合物对半胱氨酸的传感研究(第五章)。其主要研究内容简介如下:1、在第二章中,设计并制备了一种新型具有聚集诱导发光特性的黄绿色磷光铱配合物[Ir(dfppy)2(phen-DPA)]PF6 和一种橙红色磷光钌配合物[Ru(phen)2(phen-DPA)](PF6)2。发现这两种配合物在含有约2%乙腈的水溶液中能够对铜离子有着高选择性淬和高灵敏的淬灭响应,低检测限分别达到65nM和150nM (9.66ppb)。通过核磁、质谱、工作曲线等一系列测试,发现两种配合物在水溶液中都是与铜离子以1:1的结合比形成络合物,相应的结合常数为2.96×104M-1和7.64×104M-1。通过可逆性实验,我们证实了两种配合物对铜离子响应的可逆性。2、为了进一步研究识别基团二甲基吡啶胺(DPA)的作用以及其数目对配合物铜离子传感性能的影响,在第三章设计并合成了辅助配体上修饰一个和两个二甲基吡啶胺(DPA)的黄绿光铱配合物 Ir(dfppy)2(bpy-DPA)]PF6和[Ir(dfppy)2(bpy-biDPA)]PF6。发现双识别基团的配合物Ir(dfppy)2(bpy-biDPA)]PF6具有优异的光物理性能,其量子效率和发光寿命分别达到了 93.83%和101.17μs,这在铱配合物中是非常罕见的。除了更好的光物理性能外,配合物Ir(dfppy)2(bpy-biDPA)]PF6对铜离子的灵敏度也优于单个识别基团的配合物(包括上一章中的两种配合物),其最低检测限达到了 13nM。通过与上一章相似的一系列测试,发现Ir(dfppy)2(bpy-biDPA)]PF6在水溶液中与铜离子是以1:2的结合比形成络合物,相应的结合常数为1.68×1011M-2。除了稳态光谱外,铜离子浓度改变也能引起Ir(dfppy)2(bpy-biDPA)]PF6瞬态光谱的明显变化,且在一定的铜离子范围内瞬态的发光寿命与铜离子浓度也成良好的线性关系,这说明配合物Ir(dfppy)2(bpy-biDPA)]PF6也可以作为基于发光寿命变化的传感器来识别和检测铜离子。3、除了金属阳离子外,铱配合物也可以用于阴离子的检测。在第四章,我们分别在配合物的辅助配体和第一配体上修饰与配体芳环共轭的碳氮双键得到两种弱磷光铱配合物。在DMF-PBS混合溶液(50 mM,pH 7.4, v/v,3:7)体系中两种探针[Ir(ppy)2(m-ipbo)]PF6和[Ir(ppydmn)2phen]PF6能够被次氯酸根离子氧化分别释放出明亮的黄绿色光和橙黄色光,其发光强度分别为原来的12和86倍。经过加入次氯酸根离子前后的质谱分析也与预计的机理一致。除此之外,在pH中性到偏碱性环境中两种配合物都对次氯酸根离子有着良好的响应。4、作为生物体内最重要的氨基酸之一,半胱氨酸在许多生命活动中起着至关重要的作用。生命体内半胱氨酸的失衡会导致多种疾病,因此,设计并制备高效的半胱氨酸探针是十分必要的。在第五章中,利用半胱氨酸巯基与烯键的迈克尔加成,将烯丙酸脂基团和共轭烯酮结构作为识别基团分别引入铱配合物中,得到[Ir(dfppy)2(o-ippa)]PF6、[Ir(dfppy)2(p-ippa)]PF6、[Ir(dfppy)2(phen-bia)]PF6和[Ir(ppyppeo)2phen]PF6。其中,配合物[Ir(dfppy)2(phen-bia)]PF6 在含有 2%乙腈的 PBS 缓冲液(pH 5-9)中能够作为“Turn-Off,型探针检测半胱氨酸,而配合物[Ir(ppyppeo)2phen]PF6则在乙腈-PBS混合溶液(乙腈体积百分比为30%,pH 4-10)中作为“Turn-On"型探针检测半胱氨酸,其相应的检测范围和最低检测分别为0～140 μM、20～250μ 和1.17 μM、2.08 μM。
[Abstract]:Transition metal complexes of iridium and ruthenium enhance spin-orbit coupling due to the heavy atom effect of their central metals, which makes it possible to cross the system between singlet and triplet states. Thus, singlet and triple excited states can be obtained simultaneously. Finally, iridium and ruthenium complexes have room temperature phosphorescence characteristics. Its advantages such as high quantum efficiency, long luminescent lifetime, large Stokes shift and adjustable luminescent wavelength have attracted wide attention. It has been widely used in organic light-emitting diodes (OLEDs), light-emitting electrochemical cells (LECs), photodynamic therapy (PDT), optical sensors and bioimaging. A novel iridium and ruthenium complex was prepared by introducing a special functional group (recognition group) to modify the first or auxiliary ligand of the complex. The phosphorescence sensing of copper ion, hypochlorite ion and cysteine was realized by using the unique photoluminescence changes produced by the coordination or chemical reaction between the recognition group and the detected compound. There are three parts in this paper. The first part is the study on the sensing of divalent copper ions by the strong phosphorescent iridium or ruthenium complexes modified with dimethylpyridylamine (DPA) as "Turn-Off" phosphorescent probes (including chapter 2, chapter 3). The second part is the weak luminescent iridium complexes containing conjugated carbon-nitrogen double bonds as "Turn-On" phosphorescence. The third part is the study of cysteine sensing by using the Michael addition between the alkene bond on the ligand and the sulfhydryl group of cysteine (Chapter 5). The main research contents are as follows: 1. In Chapter 2, a new kind of cysteine sensing complex was designed and prepared. A yellow-green phosphorescent iridium complex [Ir (dfppy) 2 (phen-DPA)] PF6 and an orange-red phosphorescent ruthenium complex [Ru (phen) 2 (phen-DPA)] (PF6) 2 with aggregation-induced luminescence were found to have high selective quenching and high sensitivity to copper ions in aqueous solutions containing about 2% acetonitrile. The results of NMR, MS and working curves show that the two complexes form complexes with copper ion at the ratio of 1:1 in aqueous solution, and the corresponding binding constants are 2.96 *104M-1 and 7.64 *104M-1. In order to further study the effect of the recognition group dimethylpyridinium amine (DPA) and the number of DPA on the sensing properties of copper ions, a yellow-green iridium complex Ir (dfppy) 2 (bpy-DPA)] PF6 and [Ir (dfppy) 2 (bpy-biDPA)] PF6 were designed and synthesized on the auxiliary ligand in chapter 3. Nowadays, the complex Ir (dfppy) 2 (bpy-biDPA)] PF6 has excellent photophysical properties, and its quantum efficiency and luminescent lifetime are 93.83% and 101.17 ugs, respectively. This is very rare in iridium complexes. The lowest detection limit of the recognition group complex (including the two complexes in the previous chapter) is 13nM. Through a series of tests similar to those in the previous chapter, it is found that the binding ratio of Ir (dfppy) 2 (bpy-biDPA)] PF6 to copper ion in aqueous solution is 1:2, and the corresponding binding constant is 1.68 *1011M-2. The change of ion concentration can also cause the obvious change of transient spectrum of Ir (dfppy) 2 (bpy-biDPA)] PF6, and the transient luminescent lifetime of the complex Ir (dfppy) 2 (bpy-biDPA)] PF6 has a good linear relationship with the concentration of copper ions in a certain range of copper ions, which indicates that the complex Ir (dfppy) 2 (bpy-biDPA)] PF6 can also be used as a sensor to identify and detect copper based on the change of luminescent lifetime. In Chapter 4, we modify the carbon-nitrogen double bond conjugated with the aromatic ring of the ligand on the auxiliary ligand and the first ligand respectively to obtain two weak phosphorescent iridium complexes. In DMF-PBS mixed solution (50 mM, pH 7.4, v/v, 3:7) two probes [Ir (ppy) 2 (m-ipbo)] PF6 and [Ir (ppydmn) 2phen] PF6 can be oxidized by hypochlorite ions to give off bright yellow-green and orange-yellow light with the luminescence intensity of 12 and 86 times respectively. The mass spectrometry analysis before and after the addition of hypochlorite ions is also consistent with the predicted mechanism. In addition, the pH neutral to alkaline environments are two compatible species. As one of the most important amino acids in organism, cysteine plays an important role in many life activities. Cysteine imbalance in vivo can lead to many diseases. Therefore, it is necessary to design and prepare efficient cysteine probes. [Ir (dfppy) 2 (o-ippa)] PF6, [Ir (dfppy) 2 (p-ippa)] PF6, [Ir (dfppy) 2 (phen-bia)] PF6, and [Ir (dfppy) 2 (phen-bia)] PF6 and [Ir (pppeo) 2phen] PF6 were synthesized by introducing the allylic acid ester group and conjugated ketene structure as recognition groups into iridium complexes, respectively. The 2% acetonitrile PBS buffer (pH 5-9) can be used as a "Turn-Off" probe to detect cysteine, while the complex [Ir (ppyppeo) 2phen] PF6 can be used as a "Turn-On" probe to detect cysteine in the acetonitrile-PBS mixed solution (the volume percentage of acetonitrile is 30%, pH 4-10), and the corresponding detection range and minimum detection are 0-140 micrometers, 20 micrometers, 20 micrometers, respectively. ~ 250 and 1.17 M, 2.08 M.
【学位授予单位】：东南大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.4;O657.3
本文编号：2251177
[Abstract]:Transition metal complexes of iridium and ruthenium enhance spin-orbit coupling due to the heavy atom effect of their central metals, which makes it possible to cross the system between singlet and triplet states. Thus, singlet and triple excited states can be obtained simultaneously. Finally, iridium and ruthenium complexes have room temperature phosphorescence characteristics. Its advantages such as high quantum efficiency, long luminescent lifetime, large Stokes shift and adjustable luminescent wavelength have attracted wide attention. It has been widely used in organic light-emitting diodes (OLEDs), light-emitting electrochemical cells (LECs), photodynamic therapy (PDT), optical sensors and bioimaging. A novel iridium and ruthenium complex was prepared by introducing a special functional group (recognition group) to modify the first or auxiliary ligand of the complex. The phosphorescence sensing of copper ion, hypochlorite ion and cysteine was realized by using the unique photoluminescence changes produced by the coordination or chemical reaction between the recognition group and the detected compound. There are three parts in this paper. The first part is the study on the sensing of divalent copper ions by the strong phosphorescent iridium or ruthenium complexes modified with dimethylpyridylamine (DPA) as "Turn-Off" phosphorescent probes (including chapter 2, chapter 3). The second part is the weak luminescent iridium complexes containing conjugated carbon-nitrogen double bonds as "Turn-On" phosphorescence. The third part is the study of cysteine sensing by using the Michael addition between the alkene bond on the ligand and the sulfhydryl group of cysteine (Chapter 5). The main research contents are as follows: 1. In Chapter 2, a new kind of cysteine sensing complex was designed and prepared. A yellow-green phosphorescent iridium complex [Ir (dfppy) 2 (phen-DPA)] PF6 and an orange-red phosphorescent ruthenium complex [Ru (phen) 2 (phen-DPA)] (PF6) 2 with aggregation-induced luminescence were found to have high selective quenching and high sensitivity to copper ions in aqueous solutions containing about 2% acetonitrile. The results of NMR, MS and working curves show that the two complexes form complexes with copper ion at the ratio of 1:1 in aqueous solution, and the corresponding binding constants are 2.96 *104M-1 and 7.64 *104M-1. In order to further study the effect of the recognition group dimethylpyridinium amine (DPA) and the number of DPA on the sensing properties of copper ions, a yellow-green iridium complex Ir (dfppy) 2 (bpy-DPA)] PF6 and [Ir (dfppy) 2 (bpy-biDPA)] PF6 were designed and synthesized on the auxiliary ligand in chapter 3. Nowadays, the complex Ir (dfppy) 2 (bpy-biDPA)] PF6 has excellent photophysical properties, and its quantum efficiency and luminescent lifetime are 93.83% and 101.17 ugs, respectively. This is very rare in iridium complexes. The lowest detection limit of the recognition group complex (including the two complexes in the previous chapter) is 13nM. Through a series of tests similar to those in the previous chapter, it is found that the binding ratio of Ir (dfppy) 2 (bpy-biDPA)] PF6 to copper ion in aqueous solution is 1:2, and the corresponding binding constant is 1.68 *1011M-2. The change of ion concentration can also cause the obvious change of transient spectrum of Ir (dfppy) 2 (bpy-biDPA)] PF6, and the transient luminescent lifetime of the complex Ir (dfppy) 2 (bpy-biDPA)] PF6 has a good linear relationship with the concentration of copper ions in a certain range of copper ions, which indicates that the complex Ir (dfppy) 2 (bpy-biDPA)] PF6 can also be used as a sensor to identify and detect copper based on the change of luminescent lifetime. In Chapter 4, we modify the carbon-nitrogen double bond conjugated with the aromatic ring of the ligand on the auxiliary ligand and the first ligand respectively to obtain two weak phosphorescent iridium complexes. In DMF-PBS mixed solution (50 mM, pH 7.4, v/v, 3:7) two probes [Ir (ppy) 2 (m-ipbo)] PF6 and [Ir (ppydmn) 2phen] PF6 can be oxidized by hypochlorite ions to give off bright yellow-green and orange-yellow light with the luminescence intensity of 12 and 86 times respectively. The mass spectrometry analysis before and after the addition of hypochlorite ions is also consistent with the predicted mechanism. In addition, the pH neutral to alkaline environments are two compatible species. As one of the most important amino acids in organism, cysteine plays an important role in many life activities. Cysteine imbalance in vivo can lead to many diseases. Therefore, it is necessary to design and prepare efficient cysteine probes. [Ir (dfppy) 2 (o-ippa)] PF6, [Ir (dfppy) 2 (p-ippa)] PF6, [Ir (dfppy) 2 (phen-bia)] PF6, and [Ir (dfppy) 2 (phen-bia)] PF6 and [Ir (pppeo) 2phen] PF6 were synthesized by introducing the allylic acid ester group and conjugated ketene structure as recognition groups into iridium complexes, respectively. The 2% acetonitrile PBS buffer (pH 5-9) can be used as a "Turn-Off" probe to detect cysteine, while the complex [Ir (ppyppeo) 2phen] PF6 can be used as a "Turn-On" probe to detect cysteine in the acetonitrile-PBS mixed solution (the volume percentage of acetonitrile is 30%, pH 4-10), and the corresponding detection range and minimum detection are 0-140 micrometers, 20 micrometers, 20 micrometers, respectively. ~ 250 and 1.17 M, 2.08 M.
【学位授予单位】：东南大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.4;O657.3
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相关期刊论文 前2条
1 叶瑞绒;谭彩萍;计亮年;毛宗万;;磷光过渡金属配合物用于生物成像及癌症治疗的研究进展[J];药学进展;2017年01期
2 张晨;关瑞麟;陈禹;计亮年;巢晖;;基于金属配合物的生物小分子发光探针研究进展[J];药学进展;2017年01期
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