基于氢键构筑的二吡啶基类的超分子晶体结构及性质
发布时间：2019-05-29 14:40
【摘要】：超分子化学主要是研究两种或两种以上的化合物通过分子间的作用力连接而成的有序的、具有特殊功能的超分子体系的科学。近年来,由于超分子化学在荧光、吸附、催化和医药等多个领域具有广阔的应用前景而引起了人们的关注。在这些分子间作用力中,氢键因为独特的方向性以及可预测性而被称为超分子化学中的“万能钥匙”。此外,含氮杂环化合物中的N原子含有孤对电子,可以轻易的接受质子而显碱性,成为氢键良好的受体,因此是晶体学家比较感兴趣的研究对象之一。而二吡啶基烯烃类及其衍生物是一类比较特殊的含氮杂环化合物,在参与自组装时常形成具有独特性质的稳定的新型超分子化合物。本文选用三种结构相似的吡啶衍生物1,2-二(4-吡啶基)乙烯(bpe)、1,4-双[(4’-吡啶基)乙烯基]苯(1,4-bpeb)和1,3-双[(4’-吡啶基)乙烯基]苯(1,3-bpeb),与不同的无机酸、有机酸、苯酚和苯醌类物质通过挥发法或溶剂热法进行自组装得到了7种超分子化合物晶体,初步研究了它们的结构、氢键对结构和热稳定性的影响,为探讨超分子化合物的自组装规律以及应用提供了重要的参考。本论文的具体研究内容如下:1. 选用1,2-二(4-吡啶基)乙烯(bpe)与多种无机酸(HCl、HBr、HI、H_3PO_4、HCl O_4、H_2SO_4)通过挥发法进行反应,最终得到了bpe与H_3PO_4、HCl O_4和H_2SO_4自组装而成的三种晶体[(C_(12)H_(14)N_(22)~(2+))(H_2PO_4~-)_2]_n(1)、[(C_(12)H_(12)N_2~(2+))(ClO_4~-)_2]_n(2)、[(C_(12)H_(12)N_2~(2+))(SO_4~(2-))·2H_2O]_n(3),通过X-单晶衍射仪测定了这三种超分子化合物的结构,并通过粉末XRD、红外光谱、拉曼光谱和差热-热重等手段对它们进行了纯度和热稳定性的分析,结果表明这三种超分子化合物具有很高的纯度和较好的热稳定性。2.选用1,4-双[(4’-吡啶基)乙烯基]苯(1,4-bpeb)与不同的苯酚(间苯三酚、四溴邻苯二酚)和苯醌(邻四氯苯醌、2,5-二羟基-3,6-二氯苯醌)进行研究,最终得到了1,4-bpe与间苯三酚、四溴邻苯二酚自组装而成的晶体[(C_(20)H_(16)N_2)_(1.5)(C_6H_6O_3)·CH_3OH]_n(4)、[(C_(20)H_(16)N_2)_2(C_6H_2Br_4O_2)_2]_n(5),通过X-单晶衍射仪测定了这两种超分子化合物的结构,并通过粉末XRD、红外光谱、拉曼光谱和差热-热重等手段对它们进行了纯度和热稳定性的分析,结果表明它们具有很高的纯度和较好的热稳定性。3.选用1,3-双[(4’-吡啶基)乙烯基]苯(1,3-bpeb)与几种常见的羧酸(对苯二甲酸、4,4’-联苯二甲酸、4,4’-二苯乙烯二羧酸、5-(3’-羧基苯氧基)间苯二甲酸)、苯酚(间苯三酚、四溴邻苯二酚)和苯醌(邻四氯苯醌、2,5-二羟基-3,6-二氯苯醌)进行研究,最后成功得到了1,3-bpeb与5-(3’-羧基苯氧基)间苯二甲酸、四溴邻苯二酚自组装而成的晶体[(C_(20)H_(17)N_2~+)(C_(15)H_9O_7~-)]_n(6)、[(C_(20)H_(16)N_2)(C_6H_2Br_4O_2)]_n(7),通过X-单晶衍射仪测定了这两种超分子化合物的结构,并通过粉末XRD、红外光谱、拉曼光谱和差热-热重等手段对它们的纯度和热稳定性进行了分析,结果表明它们具有很高的纯度和较好的热稳定性。
[Abstract]:The supramolecular chemistry is an ordered, super-molecular system with special function, which is formed by the connection of two or more compounds through the force between the molecules. In recent years, the super-molecular chemistry has a wide application prospect in many fields such as fluorescence, adsorption, catalysis and medicine. In these intermolecular forces, hydrogen bonds are referred to as "all-energy key" in supramolecular chemistry due to unique directionality and predictability. In addition, the N atom in the nitrogen-containing heterocyclic compound contains a lone pair of electrons, can be easily accepted by the protons and is alkaline, and is a good acceptor for hydrogen bonding, and is therefore one of the research objects of which the crystallographer is more interested. The divaricotinoids and their derivatives are a kind of relatively special nitrogen-containing heterocyclic compound, and form a stable novel supramolecular compound with unique properties at the time of the self-assembly. 1,4-bis[(4 '-[4'-[4 '-[4'-[4 '-[4'-[4 '-[4'-bpab) vinyl] benzene (1,3-bpab) and 1,3-bis[(4 '-bpab) vinyl] benzene (1,3-bpab), which are similar to three structures, are selected from different inorganic acids, organic acids, The effect of the structure and hydrogen bond on the structure and thermal stability of the 7 supermolecular compound crystals was studied by the evaporation method or solvothermal method. The self-assembly rule and the application of the supramolecular compound were also discussed. The specific content of this thesis is as follows:1. The three kinds of crystal[(C _ (12) H _ (14) N _ (22) ~ (2 +)) (H _ 2PO _ 4 ~-) _ 2] _ n (1),[(C _ (12) H _ (12) N _ 2 ~ (2 +)) (ClO _ 4 ~-) _ 2] _ n (2),[(C _ (12) H _ (12) N _ 2 ~ (2 +)) (SO _ 4 ~-) _ 2] _ n (2),[(C _ (12) H _ (12) N _ 2 ~ (2 +)) (SO _ 4 ~ (2-)) 路 2H _ 2O The structure of these three supermolecular compounds was determined by X-single crystal diffractometer, and the purity and thermal stability of the three supermolecular compounds were analyzed by means of powder XRD, IR, Raman and differential thermal-thermogravimetry. The results show that the three supermolecular compounds have high purity and good thermal stability. 1,4-bis[(4 '-phenyl) vinyl] benzene (1,4-bpab) was used to study with different phenol (phloroglucinol, tetrabromocatechol) and benzene (o-tetrachlorobenzene, 2,5-dihydroxy-3,6-dichlorobenzene), and finally, 1,4-bpe and phloroglucinol were obtained. The crystal[(C _ (20) H _ (16) N _ 2) _ (1.5) (C _ 6H _ 6O _ 3) 路 CH _ 3OH] _ n (4),[(C _ (20) H _ (16) N _ 2) _ 2 (C _ 6H _ 2Br _ 4O _ 2) _ 2] _ n (5) obtained from the self-assembly of tetrabromobacol, the structure of these two supermolecular compounds was determined by X-single-crystal diffractometer, and the structure of these two supermolecular compounds was measured by X-single-crystal diffractometer, The analysis of the purity and thermal stability of them was carried out by means of Raman spectroscopy and differential thermal-thermogravimetry. The results show that they have high purity and good thermal stability. 4,4 '-biphenyldicarboxylic acid, 4,4'-diphenylethylene digluconate,5-(3 '-phenyl-phenoxy) isophthalic acid), phenol (phloroglucinol, tetrabromocatechol) and benzene benzene (o-tetrachlorobenzene, 2,5-dihydroxy-3,6-dichlorobenzene), The crystal[(C _ (20) H _ (17) N _ 2 ~ +) (C _ (15) H _ 9O _ 7 ~-)] _ n (6),[(C _ (20) H _ (16) N _ 2) (C _ 6H _ 2Br _ 4O _ 2)] _ n (7) obtained from the self-assembly of 1,3-bpab and 5-(3 '-phenyl-phenoxy) isophthalic acid and tetrabroil-catechol were successfully obtained, and the structure of these two supermolecular compounds was measured by X-single-crystal diffractometer, and the structure of these two supermolecular compounds was measured by the X-single-crystal diffractometer, The purity and thermal stability of them are analyzed by Raman spectroscopy and differential thermal-thermogravimetry. The results show that they have high purity and good thermal stability.
【学位授予单位】：河南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.3
本文编号：2488000
[Abstract]:The supramolecular chemistry is an ordered, super-molecular system with special function, which is formed by the connection of two or more compounds through the force between the molecules. In recent years, the super-molecular chemistry has a wide application prospect in many fields such as fluorescence, adsorption, catalysis and medicine. In these intermolecular forces, hydrogen bonds are referred to as "all-energy key" in supramolecular chemistry due to unique directionality and predictability. In addition, the N atom in the nitrogen-containing heterocyclic compound contains a lone pair of electrons, can be easily accepted by the protons and is alkaline, and is a good acceptor for hydrogen bonding, and is therefore one of the research objects of which the crystallographer is more interested. The divaricotinoids and their derivatives are a kind of relatively special nitrogen-containing heterocyclic compound, and form a stable novel supramolecular compound with unique properties at the time of the self-assembly. 1,4-bis[(4 '-[4'-[4 '-[4'-[4 '-[4'-[4 '-[4'-bpab) vinyl] benzene (1,3-bpab) and 1,3-bis[(4 '-bpab) vinyl] benzene (1,3-bpab), which are similar to three structures, are selected from different inorganic acids, organic acids, The effect of the structure and hydrogen bond on the structure and thermal stability of the 7 supermolecular compound crystals was studied by the evaporation method or solvothermal method. The self-assembly rule and the application of the supramolecular compound were also discussed. The specific content of this thesis is as follows:1. The three kinds of crystal[(C _ (12) H _ (14) N _ (22) ~ (2 +)) (H _ 2PO _ 4 ~-) _ 2] _ n (1),[(C _ (12) H _ (12) N _ 2 ~ (2 +)) (ClO _ 4 ~-) _ 2] _ n (2),[(C _ (12) H _ (12) N _ 2 ~ (2 +)) (SO _ 4 ~-) _ 2] _ n (2),[(C _ (12) H _ (12) N _ 2 ~ (2 +)) (SO _ 4 ~ (2-)) 路 2H _ 2O The structure of these three supermolecular compounds was determined by X-single crystal diffractometer, and the purity and thermal stability of the three supermolecular compounds were analyzed by means of powder XRD, IR, Raman and differential thermal-thermogravimetry. The results show that the three supermolecular compounds have high purity and good thermal stability. 1,4-bis[(4 '-phenyl) vinyl] benzene (1,4-bpab) was used to study with different phenol (phloroglucinol, tetrabromocatechol) and benzene (o-tetrachlorobenzene, 2,5-dihydroxy-3,6-dichlorobenzene), and finally, 1,4-bpe and phloroglucinol were obtained. The crystal[(C _ (20) H _ (16) N _ 2) _ (1.5) (C _ 6H _ 6O _ 3) 路 CH _ 3OH] _ n (4),[(C _ (20) H _ (16) N _ 2) _ 2 (C _ 6H _ 2Br _ 4O _ 2) _ 2] _ n (5) obtained from the self-assembly of tetrabromobacol, the structure of these two supermolecular compounds was determined by X-single-crystal diffractometer, and the structure of these two supermolecular compounds was measured by X-single-crystal diffractometer, The analysis of the purity and thermal stability of them was carried out by means of Raman spectroscopy and differential thermal-thermogravimetry. The results show that they have high purity and good thermal stability. 4,4 '-biphenyldicarboxylic acid, 4,4'-diphenylethylene digluconate,5-(3 '-phenyl-phenoxy) isophthalic acid), phenol (phloroglucinol, tetrabromocatechol) and benzene benzene (o-tetrachlorobenzene, 2,5-dihydroxy-3,6-dichlorobenzene), The crystal[(C _ (20) H _ (17) N _ 2 ~ +) (C _ (15) H _ 9O _ 7 ~-)] _ n (6),[(C _ (20) H _ (16) N _ 2) (C _ 6H _ 2Br _ 4O _ 2)] _ n (7) obtained from the self-assembly of 1,3-bpab and 5-(3 '-phenyl-phenoxy) isophthalic acid and tetrabroil-catechol were successfully obtained, and the structure of these two supermolecular compounds was measured by X-single-crystal diffractometer, and the structure of these two supermolecular compounds was measured by the X-single-crystal diffractometer, The purity and thermal stability of them are analyzed by Raman spectroscopy and differential thermal-thermogravimetry. The results show that they have high purity and good thermal stability.
【学位授予单位】：河南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.3
【参考文献】
相关博士学位论文 前1条
1 丁雪华;基于氢键构筑的含氮杂环超分子晶体结构及其理论研究[D];南京邮电大学;2015年
相关硕士学位论文 前3条
1 彭翠;氢键微观键合行为研究[D];大连理工大学;2011年
2 许方亮;基于氢键构筑的含氮、硫化合物研究[D];青岛科技大学;2010年
3 侯广峰;含氮杂环化合物基于氢键构筑的超分子晶体结构的研究[D];黑龙江大学;2007年
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