新型離子型銥、釕配合物光電材料的制備及其傳感性能的研究
發(fā)布時(shí)間：2018-09-19 20:00
【摘要】：過(guò)渡金屬銥、釕配合物由于其中心金屬的重原子效應(yīng)增強(qiáng)了自旋-軌道耦合作用,使得單線態(tài)和三線態(tài)之間的系間竄越成為可能,從而同時(shí)得到單重激發(fā)態(tài)和三重激發(fā)態(tài),最終導(dǎo)致銥、釕配合物具有室溫磷光的特性。磷光銥、釕配合物由于其具有較高的發(fā)光量子效率、較長(zhǎng)的發(fā)光壽命、大的斯托克斯位移和易調(diào)節(jié)的發(fā)光波長(zhǎng)等優(yōu)點(diǎn)受到人們廣泛的關(guān)注,并且在有機(jī)發(fā)光二極管(OLEDs )、發(fā)光電化學(xué)池(LECs )、光動(dòng)力療法(PDT)、光學(xué)傳感器和生物成像等領(lǐng)域有了一定的應(yīng)用。本文通過(guò)化學(xué)鍵引入特殊官能團(tuán)(識(shí)別基團(tuán))修飾配合物的第一或輔助配體得到新型銥、釕配合物,利用識(shí)別基團(tuán)與被檢測(cè)物配位或化學(xué)反應(yīng)產(chǎn)生的獨(dú)特光致發(fā)光變化來(lái)實(shí)現(xiàn)對(duì)銅離子、次氯酸根離子和半胱氨酸的磷光傳感。本論文內(nèi)容分為三個(gè)部分,第一部分是修飾離子捕獲基團(tuán)二甲基吡啶胺(DPA)的強(qiáng)磷光銥或釕配合物作為“Turn-Off"型磷光探針對(duì)二價(jià)銅離子傳感的研究(包括第二章、第三章)。第二部分是含有共軛碳氮雙鍵結(jié)構(gòu)的弱發(fā)光銥配合物作為“Turn-On”型磷光傳感器對(duì)次氯酸根離子光致發(fā)光傳感研究(第四章)。第三部分是利用配體上的烯鍵與半胱氨酸的巰基之間的邁克爾加成來(lái)進(jìn)行新型配合物對(duì)半胱氨酸的傳感研究(第五章)。其主要研究?jī)?nèi)容簡(jiǎn)介如下:1、在第二章中,設(shè)計(jì)并制備了一種新型具有聚集誘導(dǎo)發(fā)光特性的黃綠色磷光銥配合物[Ir(dfppy)2(phen-DPA)]PF6 和一種橙紅色磷光釕配合物[Ru(phen)2(phen-DPA)](PF6)2。發(fā)現(xiàn)這兩種配合物在含有約2%乙腈的水溶液中能夠?qū)︺~離子有著高選擇性淬和高靈敏的淬滅響應(yīng),低檢測(cè)限分別達(dá)到65nM和150nM (9.66ppb)。通過(guò)核磁、質(zhì)譜、工作曲線等一系列測(cè)試,發(fā)現(xiàn)兩種配合物在水溶液中都是與銅離子以1:1的結(jié)合比形成絡(luò)合物,相應(yīng)的結(jié)合常數(shù)為2.96×104M-1和7.64×104M-1。通過(guò)可逆性實(shí)驗(yàn),我們證實(shí)了兩種配合物對(duì)銅離子響應(yīng)的可逆性。2、為了進(jìn)一步研究識(shí)別基團(tuán)二甲基吡啶胺(DPA)的作用以及其數(shù)目對(duì)配合物銅離子傳感性能的影響,在第三章設(shè)計(jì)并合成了輔助配體上修飾一個(gè)和兩個(gè)二甲基吡啶胺(DPA)的黃綠光銥配合物 Ir(dfppy)2(bpy-DPA)]PF6和[Ir(dfppy)2(bpy-biDPA)]PF6。發(fā)現(xiàn)雙識(shí)別基團(tuán)的配合物Ir(dfppy)2(bpy-biDPA)]PF6具有優(yōu)異的光物理性能,其量子效率和發(fā)光壽命分別達(dá)到了 93.83%和101.17μs,這在銥配合物中是非常罕見(jiàn)的。除了更好的光物理性能外,配合物Ir(dfppy)2(bpy-biDPA)]PF6對(duì)銅離子的靈敏度也優(yōu)于單個(gè)識(shí)別基團(tuán)的配合物(包括上一章中的兩種配合物),其最低檢測(cè)限達(dá)到了 13nM。通過(guò)與上一章相似的一系列測(cè)試,發(fā)現(xiàn)Ir(dfppy)2(bpy-biDPA)]PF6在水溶液中與銅離子是以1:2的結(jié)合比形成絡(luò)合物,相應(yīng)的結(jié)合常數(shù)為1.68×1011M-2。除了穩(wěn)態(tài)光譜外,銅離子濃度改變也能引起Ir(dfppy)2(bpy-biDPA)]PF6瞬態(tài)光譜的明顯變化,且在一定的銅離子范圍內(nèi)瞬態(tài)的發(fā)光壽命與銅離子濃度也成良好的線性關(guān)系,這說(shuō)明配合物Ir(dfppy)2(bpy-biDPA)]PF6也可以作為基于發(fā)光壽命變化的傳感器來(lái)識(shí)別和檢測(cè)銅離子。3、除了金屬陽(yáng)離子外,銥配合物也可以用于陰離子的檢測(cè)。在第四章,我們分別在配合物的輔助配體和第一配體上修飾與配體芳環(huán)共軛的碳氮雙鍵得到兩種弱磷光銥配合物。在DMF-PBS混合溶液(50 mM,pH 7.4, v/v,3:7)體系中兩種探針[Ir(ppy)2(m-ipbo)]PF6和[Ir(ppydmn)2phen]PF6能夠被次氯酸根離子氧化分別釋放出明亮的黃綠色光和橙黃色光,其發(fā)光強(qiáng)度分別為原來(lái)的12和86倍。經(jīng)過(guò)加入次氯酸根離子前后的質(zhì)譜分析也與預(yù)計(jì)的機(jī)理一致。除此之外,在pH中性到偏堿性環(huán)境中兩種配合物都對(duì)次氯酸根離子有著良好的響應(yīng)。4、作為生物體內(nèi)最重要的氨基酸之一,半胱氨酸在許多生命活動(dòng)中起著至關(guān)重要的作用。生命體內(nèi)半胱氨酸的失衡會(huì)導(dǎo)致多種疾病,因此,設(shè)計(jì)并制備高效的半胱氨酸探針是十分必要的。在第五章中,利用半胱氨酸巰基與烯鍵的邁克爾加成,將烯丙酸脂基團(tuán)和共軛烯酮結(jié)構(gòu)作為識(shí)別基團(tuán)分別引入銥配合物中,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 緩沖液(pH 5-9)中能夠作為“Turn-Off,型探針檢測(cè)半胱氨酸,而配合物[Ir(ppyppeo)2phen]PF6則在乙腈-PBS混合溶液(乙腈體積百分比為30%,pH 4-10)中作為“Turn-On"型探針檢測(cè)半胱氨酸,其相應(yīng)的檢測(cè)范圍和最低檢測(cè)分別為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.
【學(xué)位授予單位】：東南大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O641.4;O657.3
本文編號(hào)：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.
【學(xué)位授予單位】：東南大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O641.4;O657.3
【參考文獻(xiàn)】
相關(guān)期刊論文 前2條
1 葉瑞絨;譚彩萍;計(jì)亮年;毛宗萬(wàn);;磷光過(guò)渡金屬配合物用于生物成像及癌癥治療的研究進(jìn)展[J];藥學(xué)進(jìn)展;2017年01期
2 張晨;關(guān)瑞麟;陳禹;計(jì)亮年;巢暉;;基于金屬配合物的生物小分子發(fā)光探針研究進(jìn)展[J];藥學(xué)進(jìn)展;2017年01期
，本文編號(hào)：2251177
本文鏈接：http://sikaile.net/kejilunwen/huaxue/2251177.html
最近更新
教材專(zhuān)著
