苯并磷杂环戊二烯及其衍生物的合成方法和光电性质研究

发布时间：2019-01-12 07:54

【摘要】：作为同族元素氮的化合物吡咯的同类物,磷杂环戊二烯由于其具有独特的光学和电化学性质,在有机材料科学领域有着广泛的用途,并受到越来越多的重视。吡咯表现为典型的芳香性,并且具有给电子的性质,而磷杂环戊二烯却具有完全不同的性质:磷杂环戊二烯表现为非常弱的芳香性,并且具有一定的电子接受能力。这是因为三配位的中心磷原子表现为四面体空间结构,使得磷原子上的孤对电子不能有效与环内的丁二烯的π电子相作用,从而导致磷杂环戊二烯体系无法具有高的芳香性,另外,环外的C-P键的σ*轨道与环内的丁二烯的π*共轭体系形成有效的σ*-π*超共轭,这明显地降低分子体系的最低空轨道能级,提高分子电子亲和势,从而具有一定的拉电子性质,这利于电子的注入和传输。磷杂环戊二烯的中心磷原子可以通过简单的化学修饰生成氧化物,硫化物,季擕盐,过渡金属配合物等,特别是氧化物和硫化物,均表现出高的化学和热力学稳定性。作为磷杂环戊二烯的一种特殊结构,苯并磷杂环戊二烯被广泛用于有机光电功能材料(有机发光二极管,太阳能电池),生物荧光探针,光致变色分子开关等方面。因此,苯并磷杂环戊二烯的合成方法受到越来越多的重视,但是与同类化合物苯并噻吩,苯并呋喃,吲哚相比较,其合成方法仍旧比较有限,本文报道通过催化方法简单高效地合成这种有前途的化合物,并在此结构基础上设计并合成同时含有磷杂环戊二烯和硅杂环戊二烯的梯形共轭分子,并对其光电性质进行研究。第一章节,首先按照不同的反应方式,介绍苯并磷杂环戊二烯的合成方法,进而阐述它们在有机半导体材料,有机光电材料,生物成像,光致变色分子开关等方面的应用。然后,阐述一些芳香环并磷杂环戊二烯分子在有机光电材料和有机分子荧光探针等方面的研究。第二章节,介绍通过Pd/Cu-双金属催化体系的方法通过分子内活化并切断C-P键,从而生成苯并磷杂环戊二烯的新方法,这种方法原料简单易的,反应一步高效,并且原子利用率高,缺点是产率相对偏低,这不仅是一种合成苯并磷杂环戊二烯的新方法,同时是新型的通过过渡金属催化切断C-P键的研究。第三章节,介绍微量空气参与,通过生成磷自由基,然后磷自由基进攻邻位炔基,分子内加成关环生成苯并磷杂环戊二烯,这种方法原料简单易得。反应不需要加入金属催化剂,也不需要额外加入添加剂,反应分离产率高,原子利用率高,一步高效,对官能团忍耐性强,并且在对环境友好。基于此反应机理,这同样是一种合成磷杂多环芳烃的行之有效的方法。第四章节,在已报到的合成苯并磷杂环戊二烯的方法基础上,设计并合成新型的同时具有磷杂环戊二烯和硅杂环戊二烯骨架的梯形共轭分子,并且对其光电特性进行研究,研究表明此类化合物的同时具有高的溶液和固态荧光量子产率,荧光集中在深蓝区,电化学分析表明此类化合具有很低的还原电势,我们对其电致发光的性质进行,结果表明此类化合物具有作为深蓝光电致发光材料发射层潜质。并且值得指出的是:部分氧化物的晶体具有力致发光的性质。
[Abstract]:As the same kind of compound of the same group of element nitrogen, P-hetero-cyclopentadiene is widely used in the field of organic material science due to its unique optical and electrochemical properties, and has been paid more and more attention. The phosphorus heterocyclopentadiene is characterized by a typical aromaticity and has the property of giving electrons, and the phosphorus heterocyclopentadiene has a completely different property: the phosphorus heterocyclopentadiene exhibits a very weak aromaticity and has a certain electronic acceptance capability. this is because the three-coordinated central phosphorus atom is represented as a tetrahedral space structure, so that the lone pair of electrons on the phosphorus atom can not function effectively with the valence electrons of the butadiene in the ring, The C-P bond of the ring and the butadiene in the ring * co-exist with the butadiene in the ring to form an effective 1 *-1 * super-coatonic system, which obviously reduces the lowest low-level orbital energy level of the molecular system, improves the molecular electronic affinity and thus has certain tensile and electronic properties, this facilitates the injection and transfer of electrons. The central phosphorus atoms of the phosphorus heterocyclopentadiene can produce oxides, sulfides, quaternary salts, transition metal complexes, and the like, in particular oxides and sulfides, by simple chemical modification, and exhibit high chemical and thermodynamic stability. As a special structure of the phosphorus hetero-cyclopentadiene, the benzo-phosphorus heterocyclopentadienols are widely used in the aspects of organic photoelectric functional materials (organic light-emitting diodes, solar cells), biological fluorescent probes, photochromic molecular switches, and the like. As a result, the synthesis method of the benzo-P-heterocyclopentadiene is more and more attention, but the synthesis method is still limited, and the synthesis method is still limited, and the synthesis method is still relatively limited, and the promising compound is simply and efficiently synthesized by a catalytic method, This structure is designed and synthesized on the basis of this structure, and the ladder-like coanda molecules containing both P-and Si-hetero-cyclopentadiene are designed and synthesized, and their photoelectric properties are studied. In the first chapter, firstly, the synthesis of the benzo-and-P-hetero-cyclopentadiene is introduced according to different reaction modes, and the application of them in the aspects of organic semiconductor material, organic photoelectric material, biological imaging, photochromic molecular switch and the like is further explained. Then, some studies on the organic photoelectric material and the fluorescent probe of organic molecules are described. in the second section, a new method for generating the benzand phosphorus heterocyclopentadienols by activating and cutting the C-P bonds in the molecule through the method of the Pd/ Cu-bimetallic catalytic system is introduced, the raw materials of the method are simple and easy, the reaction is one-step high-efficiency, and the atom utilization rate is high, and the defect is that the yield is relatively low, This is not only a new method for synthesizing benzo-P-, but also a new method for cutting C-P by transition metal. In the third chapter, the participation of trace air is introduced, the phosphorus free radicals are generated, then the phosphorus free radicals attack the o-position alkynyl group, and the intramolecular addition-off ring is used for generating the benzo-and-phosphorus-hetero-cyclopentadiene, and the method has the advantages of simple and easy-to-obtain raw materials. the reaction does not need to be added with the metal catalyst, and the addition of the additive is not required, the reaction separation yield is high, the atom utilization rate is high, the one-step high-efficiency is high, the resistance to the functional group is strong, and the environment-friendly is environment-friendly. Based on this reaction mechanism, this is also an effective method for the synthesis of a phosphorus-heteropolycyclic aromatic hydrocarbon. In the fourth chapter, on the basis of the reported method of synthesizing the benzene and the phosphorus hetero-cyclopentadiene, a novel ladder-type coanda molecule with both a phosphorus-and a silicon-heterocyclopentadiene skeleton is designed and synthesized, and the photoelectric characteristics thereof are studied, The results show that the compound has high solution and solid-state fluorescence quantum yield, the fluorescence is concentrated in the deep blue region, the electrochemical analysis shows that the combination has a very low reduction potential, The results show that the compound has the potential to be used as the light-emitting layer of the deep blue light-emitting material. and it is noted that the crystal of the partial oxide has the property of force-induced luminescence.
【学位授予单位】：郑州大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O627.51

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