本文關(guān)鍵詞： 有機(jī)共軛熒光材料 光致發(fā)光 電致變色 聚噻吩衍生物 BODIPY熒光化合物 鈍化劑　出處：《南京大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：有機(jī)共軛熒光材料具有光電性能優(yōu)異、環(huán)境友好和生物相容性好等優(yōu)點(diǎn),在電致變色、化學(xué)/生物傳感器、有機(jī)太陽(yáng)能電池、生物醫(yī)學(xué)成像和離子檢測(cè)等領(lǐng)域有著廣泛的應(yīng)用。此外,有機(jī)共軛熒光材料還具有物理化學(xué)性質(zhì)穩(wěn)定、結(jié)構(gòu)易于修飾和容易加工等特點(diǎn),由此引起了科學(xué)界更廣泛的研究興趣。設(shè)計(jì)并制備結(jié)構(gòu)新穎和綜合性能優(yōu)異的有機(jī)共軛熒光材料已經(jīng)成為當(dāng)前熒光材料領(lǐng)域的研究熱點(diǎn)之一。本論文以聚噻吩和BODIPY衍生物作為研究對(duì)象,對(duì)有機(jī)共軛熒光材料的設(shè)計(jì)、合成及其光學(xué)、電化學(xué)等相關(guān)性質(zhì)進(jìn)行了系統(tǒng)研究。在合成含噻吩和吲哚結(jié)構(gòu)的共軛寡聚物及其光致發(fā)光和電致變色性質(zhì)的研究、含吲哚的BODIPY熒光物質(zhì)的合成及其性質(zhì)研究以及尺寸可調(diào)的光致發(fā)光聚吡咯納米微球/點(diǎn)的制備及其性質(zhì)研究等方面進(jìn)行了探索,并取得了如下研究結(jié)果:(1)含噻吩和吲哚結(jié)構(gòu)的共軛寡聚物的合成及其光致發(fā)光和電致變色性質(zhì)的研究設(shè)計(jì)合成了一系列具有吲哚和噻吩結(jié)構(gòu)的新型功能單體及其對(duì)應(yīng)的寡聚物,通過(guò)NMR、GPC、FTIR和TGA確認(rèn)了它們的結(jié)構(gòu)。研究結(jié)果表明,增加共軛聚合物的吲哚數(shù)量和密度以及延長(zhǎng)吲哚部分N上烷基鏈的長(zhǎng)度可影響共軛結(jié)構(gòu)的π-π堆積相互作用,從而降低能隙和導(dǎo)致不同的光譜現(xiàn)象,同時(shí)可提高這些寡聚物的熱穩(wěn)定性。這些結(jié)果給我們提供了一個(gè)有效的方法來(lái)預(yù)測(cè)、調(diào)整分子軌道能級(jí)并進(jìn)而合成具有優(yōu)良發(fā)光性能的熒光材料�；诠丫畚颬3的電致變色器件顯示出新穎的電致變色現(xiàn)象,隨電壓增加呈現(xiàn)出紅、黃、綠和棕褐色的四種顏色變化,表明其具有作為優(yōu)異電致變色材料的潛力。此外,P3在Zn2+的選擇性檢測(cè)方面表現(xiàn)出優(yōu)良的靈敏性,在作為化學(xué)熒光傳感試劑方面也具有潛在的應(yīng)用價(jià)值。(2)含吲哚的BODIPY熒光化合物的合成及其性質(zhì)研究設(shè)計(jì)合成了一系列BODIPY的8-位含有吲哚結(jié)構(gòu)的新型功能熒光化合物c1-c6,通過(guò)NMR、FTIR和MS確認(rèn)了它們的結(jié)構(gòu)。對(duì)c3和c5的晶體結(jié)構(gòu)解析和光譜性質(zhì)測(cè)試表明,反向平行的BODIPY核心結(jié)構(gòu)使c3分子之間存在著一定程度的π-π相互作用,提高了熒光量子效率;c5由于噻吩環(huán)的引入與吲哚環(huán)形成大的平面結(jié)構(gòu),使其與BODIPY核心結(jié)構(gòu)之間的二面角變小,導(dǎo)致噻吩環(huán)和吲哚環(huán)的自由旋轉(zhuǎn)程度變大,分子內(nèi)電子的振動(dòng)弛豫過(guò)程和能量?jī)?nèi)轉(zhuǎn)換消耗能量變多,從而降低了熒光量子效率。制備得到的BODIPY化合物在不同極性溶劑里的測(cè)試結(jié)果和結(jié)構(gòu)分析表明,正溶致動(dòng)力學(xué)效應(yīng)、供吸電子效應(yīng)、空間位阻效應(yīng)和溶劑化作用等因素共同導(dǎo)致它們具有不同的熒光量子效率和光譜現(xiàn)象。理論計(jì)算和CV結(jié)果表明,吸電子基團(tuán)有利于降低化合物的能隙;供電子基團(tuán)有利于提高化合物的能隙。由于NO2和NH2的影響,c3和c6對(duì)pH的變化比較敏感,其余的c1、c2、c4和c5在不同pH條件下都比較穩(wěn)定,這可歸結(jié)于c1、c2、c4和c5這四個(gè)化合物中吲哚環(huán)上的N與化合物母體上與B原子配位后的N相比,更易于發(fā)生質(zhì)子化和去質(zhì)子化反應(yīng);此外,F原子與BODIPY核心結(jié)構(gòu)之間形成的氫鍵會(huì)抑制強(qiáng)堿性條件下對(duì)氟硼配位的破壞也是原因之一。所制備的BODIPY化合物具有物理化學(xué)性質(zhì)穩(wěn)定、生物毒性低以及熒光強(qiáng)度的對(duì)數(shù)與化合物所處溶劑粘度的對(duì)數(shù)呈良好的線性關(guān)系等特點(diǎn),在細(xì)胞成像方面表現(xiàn)出很好的應(yīng)用效果,有望在細(xì)胞顯影和測(cè)試細(xì)胞內(nèi)粘度變化從而進(jìn)行疾病診斷等方面體現(xiàn)其實(shí)際應(yīng)用價(jià)值。(3)尺寸可調(diào)的光致發(fā)光聚吡咯納米微球/點(diǎn)的制備及其性質(zhì)研究利用m-CPBA作為氧化劑,以乙醇作溶劑,成功地制備了直徑為20nm的聚吡咯納米球。所制得的聚吡咯納米球具有發(fā)射波長(zhǎng)依賴激發(fā)波長(zhǎng)的特點(diǎn)和在不同的離子條件下物理化學(xué)穩(wěn)定性好的優(yōu)點(diǎn)。通過(guò)不同結(jié)構(gòu)的鈍化劑如PEG2000、TTDDA和EDA對(duì)其表面功能化以后,熒光量子效率從最初的2.2%分別提高到了3.1%、13.3%和 40%。TEM、DLS、UV和CV的結(jié)果表明,經(jīng)過(guò) PEG2000、TTDDA和EDA對(duì)聚吡咯納米球的表面鈍化后,可以分別得到相應(yīng)的直徑為5.5 nm、4.5 nm和3 nm的納米點(diǎn),并且降低的樣品的粒子尺寸與降低的能隙和增加的熒光壽命相一致。所制備的聚吡咯納米球/點(diǎn)具有物理化學(xué)性質(zhì)穩(wěn)定、抗光漂白能力強(qiáng)和生物毒性低等特點(diǎn),在細(xì)胞成像和熒光墨水方面表現(xiàn)出很好的應(yīng)用效果,有望在相關(guān)方面的高科技領(lǐng)域體現(xiàn)其實(shí)際應(yīng)用價(jià)值。
[Abstract]:Organic conjugated fluorescent material has excellent photoelectric performance, good compatibility and environmental friendly creatures in electrochromic, chemical / biological sensors, organic solar cells, the field of biomedical imaging and ion detection has been widely used. In addition, organic conjugated fluorescent material has stable physical and chemical properties, the structure is easy to modify and easy the processing characteristics of the resulting research interest to the wider scientific community. The design and preparation of novel structure and excellent properties of organic conjugated fluorescent material has become one of the hot researches in the field of fluorescent material. In this paper, polythiophene and BODIPY derivatives as the research object, the design of organic conjugated fluorescent material, and its synthesis the optical and electrochemical properties were studied. The polymers containing thiophene and indole synthesis of conjugated oligomeric structure and its photoluminescence and electrochromic Study on color properties, BODIPY fluorescent material containing indole synthesis and its properties and size tunable photoluminescence of polypyrrole nanoparticles / preparation and properties research aspects are explored, and the results obtained are as follows: (1) the synthesis of conjugated oligomers containing thiophene and indole dimer and its structure photoluminescence and electrical design on the photochromic properties of the synthesis of a series of indole and thiophene structure of novel functional monomers and their corresponding oligomers, through NMR, GPC, FTIR and TGA confirmed their structure. The results show that the increase of the density and quantity of indole conjugated polymers and extend the indole part N the length of alkyl chain can affect the conjugate structure of Pi Pi stacking interactions, thus reducing the gap and lead to different spectrum phenomenon, also can improve the thermal stability of these oligomers. These results provide us An effective method to predict, adjust the molecular orbital and synthesis of fluorescent material has excellent luminescent properties. The oligomers of P3 electrochromic devices exhibit novel electrochromic phenomena based on the show red, with the increase in the voltage of four kinds of yellow, green and brown color change, shows as excellent electrochromic materials potential. In addition, P3 showed excellent sensitivity in the selectivity of Zn2+ detection, but also has potential applications in chemical sensing. As fluorescence reagent (2) synthesis and Properties Study on the design of BODIPY fluorescent compounds containing indole synthesis a series of BODIPY 8- containing indole structure new functional fluorescent compounds by NMR, FTIR and C1-C6, MS confirmed their structure. The crystal structure analysis and spectral properties of C3 and C5 tests show that the BODIPY core structure of antiparallel C3 molecules Between there is a certain degree of pi pi interactions, improve the fluorescence quantum efficiency; C5 due to the introduction of thiophene ring and the indole ring formation plane structure, the dihedral angle between BODIPY core structure and smaller, cause the spin degree of freedom thiophene ring and indole ring change, intramolecular vibrational relaxation of electrons relaxation process and energy conversion energy consumption, thereby reducing the fluorescence quantum efficiency. The test results in different polar solvents and structure analysis of BODIPY compounds prepared showed positive solvatokinetic effect, for the electron withdrawing effect, steric effect and solvent effect and other factors cause them to have different the fluorescence quantum efficiency and spectral phenomenon. The theoretical calculation and the results of CV showed that the electron withdrawing groups can help to reduce the gap compound; electron donating group is conducive to the improvement of energy gap compounds. Due to NO2 and NH2. Ring, is more sensitive to changes in C3 and C6 to pH, the rest of the C1, C2, C4 and C5 in different pH conditions are relatively stable, and it can be attributed to C1, C2, C4 and C5 of the four compounds N and compounds indole ring on the matrix and B atoms after compared to N it is easy to occur, the protonation and deprotonation reaction; in addition, formed between the F atom and the BODIPY core structure of the hydrogen will suppress the strong alkaline conditions of fluorine boron coordination failure is one of the reasons. The preparation of BODIPY compounds with stable physical and chemical properties, low toxicity and logarithm and the fluorescence intensity of the compounds the solvent viscosity showed a good linear relationship and other characteristics, showing good application effect in cell imaging, is expected to change in the viscosity of cells developing and testing cells to diagnose the disease and other aspects reflect its practical value. (3) light adjustable size induced Light / polypyrrole nanoparticles preparation and properties using m-CPBA as oxidant, with ethanol as solvent, was prepared successfully with diameter of polypyrrole nanospheres 20nm. The polypyrrole nano ball with emission wavelength depend on the excitation wavelength and advantages in ion under the conditions of different physical and chemical stability of the through the structure of different passivation agents such as PEG2000, TTDDA and EDA on the surface of functionalized fluorescent quantum efficiency were increased from the initial 2.2% to 3.1%, 13.3% and 40%.TEM, DLS, UV and CV showed that, after PEG2000, TTDDA and EDA on the surface passivation of polypyrrole nanoparticles can be obtained, respectively the diameter of 5.5 nm, 4.5 nm and 3 nm nano, and reduced the particle size and reduce the consistent gap and the increase of the fluorescence lifetime. The polypyrrole nanospheres prepared with chemical / physical It has stable properties, strong resistance to photobleaching and low toxicity. It shows good application results in cell imaging and fluorescent ink. It is expected to reflect its practical application in related high-tech fields.

【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ422

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