本文關鍵詞：灣位官能化雙親性POSS-PDI納米雜化材料的合成及其自組裝行為的研究　出處：《東華大學》2015年碩士論文　論文類型：學位論文

  更多相關文章： 灣位 功能化 POSS 傒酰亞胺 自組裝

【摘要】：傒酰亞胺（Perylene dimide，PDI）是具有優(yōu)異穩(wěn)定性和強烈光物理特性的稠環(huán)芳烴，因具有極強的π-π相互作用，能夠自發(fā)的形成有序堆積體，是獨特的分子電學材料，在太陽能電池，生物熒光探針，化學感應器等諸多領域的研究中受到廣泛的關注。其分子結構及其固體材料的凝聚態(tài)結構是決定PDI類材料光物理性質及其應用性能的關鍵，其中通過親疏水作用調控PDI的凝聚態(tài)結構是研究熱點和重點之一。 籠形倍半硅氧烷POSS是具有豐富烷基鏈、直徑（約0.78nm）的疏水性無機納米粒子，可作為大取代基改善PDI的溶解性和限制π-π堆砌；三乙二醇（TEG）是含有親水性基團的線性結構物質，且末端羥基可與溶劑形成氫鍵或可作為進一步改性的官能團。將納米顆粒POSS和TEG同時引入PDI分子中，在上述多重因素影響下，PDI的自組裝行為會如何？為此本文合成了側基均為POSS而灣位分別為H（未取代）、Br和三乙二醇（TEG）的三種POSS-PDI-POSS分子：POSS-PDIH-POSS、POSS-PDIBr-POSS、POSS-PDITEG-POSS，研究了PDI分子的溶液自組裝行為、自組裝產物的凝聚態(tài)結構和晶態(tài)下光物理性質，以期考察和理解在多重相互作用下PDI分子的溶液自組裝。主要研究成果如下： 1.以（PTCDA）為原料，通過先灣位溴代后側基POSS取代的方法合成POSS-PDIBr-POSS，使用柱層析分離得到灣位1,6和1,7取代POSS-PDIBr-POSS產物（同一Rf值），然后再通過重復長晶體的方法得到了灣位1,7取代POSS-PDIBr-POSS的晶體。以灣位1,7取代POSS-PDIBr-POSS為原料，在K2CO3和十八冠六醚的催化體系催化下合成了灣位三乙二醇取代的POSS-PDITEG-POSS，使用層析柱和長晶體得到純凈的灣位1,7取代的POSS-PDITEG-POSS。通過FTIR、NMR和MALDI-TOF等表征明晰了化合物的結構和高純度，為后續(xù)自組裝行為的研究打下了基礎。 2.紫外-可見吸收光光譜和熒光光譜是表征PDI分子溶液自組裝行為的通用手段，其測試結果的準確性、可靠性和易獲取性，在很大程度上依賴于分子結構和溶劑的種類。為此本研究首先系統(tǒng)考察了溶劑的種類、溶液濃度、復合溶劑組成對POSS-PDI-POSS自組裝行為的影響，并據(jù)此建立了一套適用于PDI快速定位溶劑、濃度等關鍵因素的方法，，包括樣品處理、溶劑性評估、選取溶劑、滴定實驗等，為探索三種分子溶液自組裝行為奠定基礎。進而比較分析了上述三種POSS-PDI-POSS分子的溶液自組裝行為。結果表明在稀溶液的單分子態(tài)下，POSS-PDITEG-POSS的0-0電子躍遷吸收峰（567nm）相比于POSS-PDIH-POSS, POSS-PDIBr-POSS（524nm，522nm）吸收紅移，而它們的熒光發(fā)射依次為589nm，543nm和550nm，說明灣位溴代和三乙二醇的取代造成傒平面扭曲，破壞了π-π相互作用，這點也可在分子模擬構型優(yōu)化和能級差計算輔助中所驗證。三個分子在己醇中均可發(fā)生自組裝，其臨界濃度分別為1.24E-6M、1.8E-4M和4.8E-4M，對POSS-PDIH-POSS, POSS-PDIBr-POSS而言，丙醇/二氧六環(huán)是理想的復合溶劑體系，而POSS-PDITEG-POSS的理想溶劑體系則為THF/水。在溶液自組裝中，三個分子均具有吸收寬化和ε0-0/ε0-1比值減小且形成二聚體的特點，但是聚集體在熒光表現(xiàn)上可知，只有POSS-PDIH-POSS具有發(fā)射，后兩者均發(fā)生顯著淬滅，說明它們形成的二聚體在構型上可能具有區(qū)別。 3.這三個分子通過相分離方法可以形成特定形貌的聚集體，熒光、偏光顯微鏡和SEM、TEM等手段表征表明，POSS-PDIH-POSS和POSS-PDIBr-POSS形成針狀晶體，在晶體中兩種分子均以二聚體為最小基元形成不連續(xù)堆砌，POSS-PDIH-POSS呈J型二聚體，POSS-PDIBr-POSS由于極大的長軸位移以至在萘環(huán)之間形成H型二聚體，這可能是POSS-PDIBr-POSS晶體具有獨特光物理性質的原因：相較于POSS-PDIH-POSS熒光發(fā)射光譜藍移和熒光量子產率低的特點，其藍移現(xiàn)象也區(qū)別于灣位溴代、側基為線性鏈的PDI的紅移。而POSS-PDITEG-POSS則形成由片狀聚集體堆砌成的球狀顆粒，高分辨率TEM下可觀察到片狀聚集體由間距為2.7nm較深色線狀條帶（納米顆粒POSS）組裝成的有序體。通過變溫FTIR和亞穩(wěn)態(tài)有序結構的形成分析，以及POSS-PDI-POSS以二聚體為基元堆砌的特點，推測其形成機理為：分子形成二聚體后首先堆砌成層，然后層層堆砌，最后由于親疏水和氫鍵等共同作用形成球狀晶體。
[Abstract]:Xi imide (Perylene dimide PDI) is a polycyclic aromatic hydrocarbon with excellent stability and strong photophysical properties, because of its strong pi pi interactions, can spontaneously form ordered accumulation, is unique in the molecular electrical materials, solar cells, biological fluorescent probes have attracted the attention of research on chemical sensors and many other fields. Its molecular structure and solid material condensed structure is the key material of PDI optical properties and application properties of the hydrophilic hydrophobic interaction, through the regulation of PDI condensed structure is a research hotspot and focus.
Silsesquioxanes POSS has rich alkyl chain, the diameter (about 0.78nm) hydrophobic inorganic nanoparticles can be used as a substitute for improving the solubility of PDI and limit tt-tt stacking; triethylene glycol (TEG) is a linear structure material containing hydrophilic groups, and terminal hydroxyl groups can form hydrogen bonds with the solvent or as a further modification of the functional groups. The nano particles of POSS and TEG at the same time, the introduction of PDI molecules, under the influence of these multiple factors, PDI self-assembly behavior will be how? This paper synthesized side groups were POSS and H respectively for the Bay (unsubstituted), Br and triethylene glycol (TEG) three POSS-PDI-POSS: POSS-PDIH-POSS, POSS-PDIBr-POSS, POSS-PDITEG-POSS molecules, the self-assembly behavior of the solution PDI molecular research, self condensed state structure and photophysical properties of crystal assembled products, in order to investigate and understand the interaction in multiple PDI molecules Self - assembly of solution. The main research results are as follows:
In 1. (PTCDA) as raw materials, through the first bay of bromo substituted side based POSS synthesis of POSS-PDIBr-POSS, using column chromatography by 1,6 and 1,7 bay to replace the POSS-PDIBr-POSS product (same Rf value), and then through the method of repeated long crystal has been 1,7 to replace the POSS-PDIBr-POSS Bay Bay in a crystal. 1,7 replaced POSS-PDIBr-POSS as raw material, the bay of triethylene glycol substituted POSS-PDITEG-POSS synthesis catalyzed by K2CO3 in the six and eighteen crown ether, using chromatography column and long crystal pure Bay 1,7 substituted POSS-PDITEG-POSS. through FTIR, NMR and MALDI-TOF were used to characterize the structures of these compounds were clear and high purity, for subsequent research the self-assembly behavior of the foundation.
2. UV Vis absorption spectroscopy and fluorescence spectroscopy is a common means of self-assembly of molecular characterization of PDI solution, the test result accuracy, reliability and accessibility, species depend on the molecular structure and solvent. This study first investigates the type of solvent, concentration, solvent effect of POSS-PDI-POSS composition on the self-assembly behavior, and established a set of suitable for PDI rapid positioning method of key factors such as solvent, concentration, solvent including sample treatment, assessment, selection of solvent, titration experiments, in order to explore the molecular self-assembly behavior of three kinds of solution to lay the foundation. Then it compares the self assembling behavior of the solution the above three kinds of POSS-PDI-POSS molecules. The results show that in single molecule in dilute solution, 0-0 electronic transition of POSS-PDITEG-POSS absorption peak (567nm) compared to POSS-PDIH-POSS, POSS-PDIBr-POS S (524nm, 522nm) absorption redshift, and their fluorescence emission were 589nm, 543nm and 550nm, indicating to replace the Bay - Bromination and triethylene glycol by Xi plane distortion, destroy the pi pi interactions, this can also be in the molecular simulation of structure optimization and energy difference calculation verification assistant. Three can be found in the hexanol in molecular self-assembly, the critical concentrations were 1.24E-6M, 1.8E-4M and 4.8E-4M, POSS-PDIH-POSS, POSS-PDIBr-POSS, alcohol / two oxygen six ring is an ideal composite solvent system, and the ideal solvent system POSS-PDITEG-POSS is THF/ water. In solution self-assembly, three molecules have wide absorption 0-0/ and 0-1 ratio decreases and the epsilon epsilon two dimer formation characteristics, but the fluorescence performance of aggregates, only POSS-PDIH-POSS has launched both significant quenching, two together they form the body configuration There can be a difference.
3. of the three molecules through the method of phase separation to form specific morphologies of aggregates, fluorescence, polarizing microscope and SEM, TEM and other measurements showed that POSS-PDIH-POSS and POSS-PDIBr-POSS formed in the crystal acicular crystal, two molecules with two dimers as least element to form a discontinuous stack, POSS-PDIH-POSS is J two dimer POSS-PDIBr-POSS due to large displacement and the long axis of the naphthalene ring is formed between the two type H dimer, which is probably the reason why the POSS-PDIBr-POSS crystal has unique photophysical properties: compared to the POSS-PDIH-POSS blue shift of fluorescence emission spectra and fluorescence quantum yield is low, the blue shift phenomenon is different from the bay a bromination, redshift side group is linear the chain of PDI. And the POSS-PDITEG-POSS is formed by spherical particles flake aggregates piled into the high resolution TEM can be observed by the sheet-like aggregate spacing is 2.7nm a darker line Take (POSS nanoparticles) were assembled into orderly. Through the analysis of the temperature dependence of the FTIR and the formation of metastable ordered structure, and the characteristics of POSS-PDI-POSS two dimer stacking as primitives, speculated that the formation mechanism is: two molecules to form a dimer after first stacking layer, then layers stack, finally due to the combined effect of hydrophobic hydrogen bond and formation of globular crystals.

【學位授予單位】：東華大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TQ241.5;TB383.1

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