多酸基光敏材料的杂化分子自组装及性能研究

发布时间：2018-01-11 21:38

本文关键词：多酸基光敏材料的杂化分子自组装及性能研究　出处：《北京化工大学》2016年硕士论文　论文类型：学位论文

【摘要】：香豆素这类天然产物在分子结构上同时含有六元杂环和羰基官能团,显示出极强的荧光潜能,研究发现可以通过分子改造,即在香豆素母体分子的苯环链上共价修饰引入其他官能团,使得到的衍生物具有不同紫外吸收波长和荧光发射波长,显示出强的荧光性能。此外该类改性后的化合物可以在紫外光和可见光照射条件下进行可逆的光聚合反应,因此可以利用这一特性,将香豆素基团与各类聚合物分子相结合,形成多种系列的“光敏感型”杂化材料,从紫外光照的波长、强度、位置及时间长短等多个角度,通过改变影响聚合产物的几大因素,使得到聚合产物展现出不同的物理化学性能,达到有效控制分子白组装的目的。多金属氧酸盐(简称多酸)是一类金属-氧簇类化合物,主要是由V、Mo、W、Nb、Ta等过渡金属元素组成,具有丰富的物理和化学性质,尤其是在电荷转移方面,拥有良好的电子离域和电荷传输性能,通过构筑以共轭型有机物为配体与多酸相结合的有机-无机杂化材料,可以将多酸广泛应用在光学发光、导电与电磁性能等方面,是一类良好的光学非线性材料。在这类化合物材料中,杂多酸阴离子作为受体来接受电子,共轭有机分子作为供体来给予电子,因而可发生给体-受体之间的电子转移。通过有机共价修饰的方法将各种功能性基团连接到多酸分子上,构筑得到的有机-无机杂化材料可以充分展示出多酸在不同研究领域的应用,使新型多酸功能材料的分析研究更加深入细致全面充分。本文一方面通过共价修饰的方法合成了基于Keggin型多酸的香豆素酰氯化衍生物杂化分子材料,对所得产物通过UV-Vis、FT-IR、核磁共振谱、ESI-MS (TOF)和元素分析等方法确认了结构,并利用紫外光谱、核磁共振光谱(1H NMR和2D COSY NMR)、凝胶渗透色谱(GPC)、电子能谱(XPS)等对这种化合物在有机溶液中的光聚合性能进行了详细的研究。另一方面在传统Anderson型多酸对称修饰的研究背景下,尝试采用新的方法合成出不对称的杂化分子,将两种对光具有不同敏感特性的分子共价修饰在Mn-Anderson型多酸两侧,探究复杂体系的光学性能,延伸扩展了多酸在光学方面的功能化应用,更加的细致完善。基于上述研究,对这种新型多酸基杂化分子在有机溶液中的光致变色特性作进一步研究,证实了具有在紫外光下聚合和可见光下解聚的可逆光敏感特性。
[Abstract]:The natural products such as coumarin contain six heterocyclic and carbonyl functional groups at the same time in the molecular structure, which shows very strong fluorescence potential, and it can be modified by molecular. In other words, the covalent modification of the benzene chain of coumarin mother molecule introduced other functional groups, so that the derivatives have different UV absorption wavelength and fluorescence emission wavelength. In addition, the modified compounds can undergo reversible photopolymerization under ultraviolet and visible light irradiation, so they can take advantage of this property. The coumarin group was combined with various kinds of polymer molecules to form a series of "photo-sensitive" hybrid materials from the wavelength, intensity, position and duration of ultraviolet light. By changing several factors which affect the polymerization products, the polymerized products show different physical and chemical properties. Polyoxometalates (polyoxometalates) are a kind of metal-oxygen cluster compounds, which are mainly composed of transition metal elements such as V _ (Mo) O _ (+) W _ (+) N _ (bN) Ta and so on. It has abundant physical and chemical properties, especially in charge transfer, and has good electron delocalization and charge transport properties. By constructing organic-inorganic hybrid materials with conjugated organic compounds as ligands and polyacids, polyacids can be widely used in optical luminescence, conductivity and electromagnetic properties. Heteropolyacid anion is a kind of good optical nonlinear material in which heteropolyacid anions are used as receptors and conjugated organic molecules are used as donors to give electrons. Therefore, electron transfer between donor and acceptor can occur, and various functional groups can be connected to polyacid molecules by organic covalent modification. The organic-inorganic hybrid materials can fully demonstrate the application of polyacids in different research fields. On the one hand, we synthesized coumarin acylchlorinated derivative hybrid molecular material based on Keggin polyacid by covalent modification. The structures of the products were confirmed by UV-Vis-FT-IR, ESI-MS TOF and elemental analysis, and UV spectra were used. 1H NMR and 2D COSY NMRA, gel permeation chromatography (GPC). The photopolymerization properties of this compound in organic solution have been studied in detail by electron dispersive spectroscopy (EDS). On the other hand, under the background of traditional Anderson type polyacid symmetry modification. An asymmetric hybrid molecule was synthesized by a new method. Two kinds of molecules with different sensitivity to light were covalently modified on the sides of Mn-Anderson polyacid to explore the optical properties of the complex system. The application of polyacid in optical functionalization is extended and improved. Based on the above research, the photochromic properties of this novel polyacid-group hybrid molecule in organic solution are further studied. The reversibility of polymerization under ultraviolet light and depolymerization under visible light has been confirmed.
【学位授予单位】：北京化工大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：TB381

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