基于氫鍵構(gòu)筑的二吡啶基類的超分子晶體結(jié)構(gòu)及性質(zhì)
發(fā)布時間：2019-05-29 14:40
【摘要】：超分子化學(xué)主要是研究兩種或兩種以上的化合物通過分子間的作用力連接而成的有序的、具有特殊功能的超分子體系的科學(xué)。近年來,由于超分子化學(xué)在熒光、吸附、催化和醫(yī)藥等多個領(lǐng)域具有廣闊的應(yīng)用前景而引起了人們的關(guān)注。在這些分子間作用力中,氫鍵因為獨特的方向性以及可預(yù)測性而被稱為超分子化學(xué)中的“萬能鑰匙”。此外,含氮雜環(huán)化合物中的N原子含有孤對電子,可以輕易的接受質(zhì)子而顯堿性,成為氫鍵良好的受體,因此是晶體學(xué)家比較感興趣的研究對象之一。而二吡啶基烯烴類及其衍生物是一類比較特殊的含氮雜環(huán)化合物,在參與自組裝時常形成具有獨特性質(zhì)的穩(wěn)定的新型超分子化合物。本文選用三種結(jié)構(gòu)相似的吡啶衍生物1,2-二(4-吡啶基)乙烯(bpe)、1,4-雙[(4’-吡啶基)乙烯基]苯(1,4-bpeb)和1,3-雙[(4’-吡啶基)乙烯基]苯(1,3-bpeb),與不同的無機酸、有機酸、苯酚和苯醌類物質(zhì)通過揮發(fā)法或溶劑熱法進行自組裝得到了7種超分子化合物晶體,初步研究了它們的結(jié)構(gòu)、氫鍵對結(jié)構(gòu)和熱穩(wěn)定性的影響,為探討超分子化合物的自組裝規(guī)律以及應(yīng)用提供了重要的參考。本論文的具體研究內(nèi)容如下:1. 選用1,2-二(4-吡啶基)乙烯(bpe)與多種無機酸(HCl、HBr、HI、H_3PO_4、HCl O_4、H_2SO_4)通過揮發(fā)法進行反應(yīng),最終得到了bpe與H_3PO_4、HCl O_4和H_2SO_4自組裝而成的三種晶體[(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),通過X-單晶衍射儀測定了這三種超分子化合物的結(jié)構(gòu),并通過粉末XRD、紅外光譜、拉曼光譜和差熱-熱重等手段對它們進行了純度和熱穩(wěn)定性的分析,結(jié)果表明這三種超分子化合物具有很高的純度和較好的熱穩(wěn)定性。2.選用1,4-雙[(4’-吡啶基)乙烯基]苯(1,4-bpeb)與不同的苯酚(間苯三酚、四溴鄰苯二酚)和苯醌(鄰四氯苯醌、2,5-二羥基-3,6-二氯苯醌)進行研究,最終得到了1,4-bpe與間苯三酚、四溴鄰苯二酚自組裝而成的晶體[(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),通過X-單晶衍射儀測定了這兩種超分子化合物的結(jié)構(gòu),并通過粉末XRD、紅外光譜、拉曼光譜和差熱-熱重等手段對它們進行了純度和熱穩(wěn)定性的分析,結(jié)果表明它們具有很高的純度和較好的熱穩(wěn)定性。3.選用1,3-雙[(4’-吡啶基)乙烯基]苯(1,3-bpeb)與幾種常見的羧酸(對苯二甲酸、4,4’-聯(lián)苯二甲酸、4,4’-二苯乙烯二羧酸、5-(3’-羧基苯氧基)間苯二甲酸)、苯酚(間苯三酚、四溴鄰苯二酚)和苯醌(鄰四氯苯醌、2,5-二羥基-3,6-二氯苯醌)進行研究,最后成功得到了1,3-bpeb與5-(3’-羧基苯氧基)間苯二甲酸、四溴鄰苯二酚自組裝而成的晶體[(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),通過X-單晶衍射儀測定了這兩種超分子化合物的結(jié)構(gòu),并通過粉末XRD、紅外光譜、拉曼光譜和差熱-熱重等手段對它們的純度和熱穩(wěn)定性進行了分析,結(jié)果表明它們具有很高的純度和較好的熱穩(wěn)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.
【學(xué)位授予單位】：河南師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.3
本文編號：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.
【學(xué)位授予單位】：河南師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.3
【參考文獻】
相關(guān)博士學(xué)位論文 前1條
1 丁雪華;基于氫鍵構(gòu)筑的含氮雜環(huán)超分子晶體結(jié)構(gòu)及其理論研究[D];南京郵電大學(xué);2015年
相關(guān)碩士學(xué)位論文 前3條
1 彭翠;氫鍵微觀鍵合行為研究[D];大連理工大學(xué);2011年
2 許方亮;基于氫鍵構(gòu)筑的含氮、硫化合物研究[D];青島科技大學(xué);2010年
3 侯廣峰;含氮雜環(huán)化合物基于氫鍵構(gòu)筑的超分子晶體結(jié)構(gòu)的研究[D];黑龍江大學(xué);2007年
，本文編號：2488000
本文鏈接：http://sikaile.net/kejilunwen/huaxue/2488000.html
最近更新
教材專著
