本文關(guān)鍵詞：氫鍵等分子間作用力構(gòu)建的杯芳烴納米管　出處：《武漢大學(xué)》2015年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 超分子化學(xué) 杯芳烴 硫雜杯芳烴 氫鍵 鹵鍵 自組裝 納米管

【摘要】：杯芳烴本身具有疏水性的空腔,能通過自身的反應(yīng)位點(diǎn)引入不同的官能團(tuán),通過主客體分子間多種非共價鍵作用力形成的超分子聚集體,在氣體吸附、模擬酶催化、藥物載體、納米材料和富勒烯化學(xué)等方面得到了廣泛的應(yīng)用。然而目前基于杯芳烴的自組裝體及其形成的納米管的報道仍然不多,對杯芳烴自組裝機(jī)理也了解甚少。本論文在實(shí)驗(yàn)室以前工作的基礎(chǔ)之上,進(jìn)一步深入地研究擁有不同構(gòu)象和不同作用位點(diǎn)的杯[4]芳烴和硫雜杯[4]芳烴通過非共價鍵作用力形成納米管的自組裝行為。第一章首先介紹了超分子化學(xué)和主客體化學(xué),接著較為詳細(xì)地介紹了杯[4]芳烴主體分子的結(jié)構(gòu)、構(gòu)象及其衍生化反應(yīng),最后總結(jié)了通過非共價鍵作用力作為驅(qū)動力,包括氫鍵、π…π堆積作用和金屬配位鍵等,形成杯[4]芳烴納米管的研究進(jìn)展。第二章合成了上緣含醛基、氰基和羧基基團(tuán)的不同構(gòu)象的杯[4]芳烴衍生物,上緣含醛基、氰基和羥基的錐式構(gòu)象的硫雜杯[4]芳烴衍生物和上緣含醛基的部分錐式構(gòu)象的硫雜杯[4]芳烴衍生物。通過最終的反應(yīng)產(chǎn)物推測出杯[4]芳烴下緣異丙基的脫去是在醛基引入到杯芳烴上緣之后進(jìn)行的。通過研究柱[5]芳烴反應(yīng)的中間產(chǎn)物并結(jié)合文獻(xiàn)分析,驗(yàn)證了Holler提出柱[5]芳烴的合成是通過陽離子反應(yīng)機(jī)理的合理性。第三章研究了沒有強(qiáng)氫鍵授受體存在的情況下,用氯仿/環(huán)己烷作為結(jié)晶溶劑,不同構(gòu)象的硫雜杯[4]芳烴衍生物的自組裝行為。與杯[4]芳烴相比,橋聯(lián)S原子取代C原子使硫雜杯[4]芳烴擁有更大的空腔,更容易形成“頭對頭,,的二聚體結(jié)構(gòu)；S原子形成的S…π和S…S等作用力能有效協(xié)助晶體進(jìn)行自組裝。結(jié)果顯示：錐式構(gòu)象的醛基硫雜杯[4]芳烴衍生物都通過分級拼接的方式形成了“頭對頭”的二聚體和蜂窩狀的納米管結(jié)構(gòu)；錐式構(gòu)象的氰基硫雜杯[4]芳烴衍生物在無法形成二聚體的情況下,通過與氯仿分子間的Cl…π、N…Cl和Cl…Cl作用力也形成了蜂窩狀的納米管結(jié)構(gòu)；部分錐式構(gòu)象的醛基硫雜杯[4]芳烴衍生物由于苯環(huán)倒置減少了環(huán)腔間的排斥,形成了“頭對頭”二聚體和蜂窩狀的納米管結(jié)構(gòu)；下緣乙酸乙酯和苯甲酰基四取代的1,3-交替構(gòu)象的硫雜杯[4]芳烴衍生物能通過S…π或S…S作用力以“肩并肩”的方式進(jìn)行連接,形成沿杯芳烴環(huán)腔堆積的納米管結(jié)構(gòu)。從這些我們可以看出,主體分子的構(gòu)象不是分子能否構(gòu)成納米管的決定因素,在分子骨架上引入適當(dāng)?shù)幕鶊F(tuán),并在合適的結(jié)晶環(huán)境下通過分子間的相互作用力能以恰當(dāng)?shù)呐帕蟹绞叫纬杉{米管。第四章研究了杯芳烴上緣存在強(qiáng)氫鍵授受體的情況下,分別用吡啶/甲醇和四氫呋喃/甲醇作為結(jié)晶溶劑,不同構(gòu)象的杯[4]芳烴羧酸衍生物(羧酸數(shù)目≥2)自組裝行為。錐式構(gòu)象的杯[4]芳烴羧酸衍生物的羧基位于杯芳烴的同一側(cè),可以與其它主體分子和溶劑分子形成不同類型的氫鍵作用力;當(dāng)同側(cè)連有羧基的苯環(huán)向環(huán)腔收縮(二面角小于30°,杯芳烴分子傾向于形成由自身的兩對羧基構(gòu)成的氫鍵二聚體結(jié)構(gòu),當(dāng)連有羧基的苯環(huán)向環(huán)外擴(kuò)張,相鄰的主體分子會形成由一對羧基間氫鍵構(gòu)成的一維波浪結(jié)構(gòu)。部分錐式和1,3-交替構(gòu)象的杯[4]芳烴羧基衍生物,由于羧基在兩側(cè),可以直接或者在溶劑的幫助下形成一維波浪形或者鏈狀的結(jié)構(gòu)。溶劑分子對自組裝行為產(chǎn)生影響,吡啶容易通過O-H…N氫鍵形成“頭對頭”的二聚體結(jié)構(gòu),主導(dǎo)分子的自組裝;四氫呋喃體現(xiàn)的是一個協(xié)助作用,填充在晶體所形成的空隙中；在缺少強(qiáng)氫鍵作用點(diǎn)的情況下,甲醇可以作為一個補(bǔ)充的氫鍵作用位點(diǎn)與主體分子間以“頭對頭”或“肩并肩”的方式相連接。第五章研究了沒有強(qiáng)氫鍵授受體和S硫原子存在的情況下,不同構(gòu)象的杯[4]芳烴衍生物的自組裝行為。由于超分子作用點(diǎn)比較少,杯芳烴在分子間的弱相互作用力,如C-H…O、C-H…π和O…π等,協(xié)助下通過分子間緊密堆積的方式形成超分子網(wǎng)絡(luò)結(jié)構(gòu)。下緣取代基的位阻效應(yīng)會影響杯[4]芳烴衍生物產(chǎn)生不同的自組裝行為。當(dāng)下緣沒有取代基時,錐式構(gòu)象的醛基杯[4]芳烴容易以分級拼接方式形成納米管；當(dāng)下緣的取代基為柔性較大的正丙基時,1,3-交替構(gòu)象杯[4]芳烴四醛分子為了有效降低相鄰分子之間的排斥力,分子發(fā)生了90°的旋轉(zhuǎn),通過兩組相互垂直的醛基形成三維的C-H…O氫鍵,沿著分子環(huán)腔方向堆積形成了一維納米通道；當(dāng)下緣的取代基為位阻較大的異丙基時,1,3-交替構(gòu)象杯[4]芳烴醛基衍生物的醛基向環(huán)腔內(nèi)收縮,分子間通過密堆積形成三維結(jié)構(gòu)；在杯[4]芳烴的上緣引入氰基或者下緣引入苯甲�；梢蕴峁┎煌愋偷某肿幼饔命c(diǎn),協(xié)助杯芳烴聚集體的生成。
[Abstract]:The calixarene cavity itself is hydrophobic, through the reaction sites themselves into different functional groups, the main object of intermolecular non covalent bond interaction of various supramolecular aggregates formed in the gas, adsorption, mimic enzyme catalysis, drug carrier, nano materials and fullerene chemistry has been widely used. However, self assembling cup the aromatic body and the formation of nanotubes is reported based on still not much, little of the calixarene self-assembly mechanism. This paper also understand based on previous work in the laboratory, further study the self-assembly behavior with different conformation and different sites of Calix [4] arene and thiacalix [4] arene through non covalent interactions to form nanotubes. The first chapter introduces the supramolecular chemistry and host guest chemistry, then describes in detail the structure of Calix [4] arene molecular structure. In the end, the effects of the non covalent bond force as the driving force, including the hydrogen bond, pi... PI stacking interactions and metal ligand bond, the advances in research on the formation of Calix [4] nanotubes. The upper edge of the second chapter containing aldehyde synthesis, calix [4] arene derivatives of different conformation of cyano group and carboxyl groups, on the border with aldehyde, cone conformation cyano and hydroxyl on the sulfur partial cone conformation of Calix [4] aromatic derivatives and the upper edge of the containing aldehyde thiacalix [4] arene derivatives. The final reaction products that remove calix [4] arene is in the lower edge of isopropyl aldehyde into after the calixarene margin. The intermediate of pillar [5] arene reaction and combined with literature analysis, verification the synthesis of Holler of pillar [5] arene through reasonable cationic reaction mechanism. The third chapter studies the strong hydrogen bond acceptor without the presence of chloroform / cyclohexane as solvent crystallization, different conformations of thia self-assembly of Calix [4] arene derivatives Behavior, compared with calix [4] arene, bridged S atoms instead of C atoms make the calix [4] aromatics have larger cavities, easier to form the "head pair", the two polymer structure, and the S formed by S atoms. PI and S... S force can effectively assist crystal self-assembly. The results showed that the sulfur aldehyde cone conformation thiacalix [4] arene derivatives through the classification mosaic and formed a "nanotube structure two dimers and honeycomb head"; the sulfur cyano cone conformation thiacalix [4] arene derivatives in not formation two dimers, with chloroform molecules Cl... PI, N... Cl and Cl... Cl force also formed a honeycomb tube structure; aldehyde sulfur part cone conformation thiacalix [4] arene derivatives of benzene ring cavity reduces the inversion due to the repulsion between, forming a nanotube structure two head to head dimer and honeycomb; the lower edge of ethyl acetate and four benzoyl substituted 1,3- alternate conformation thiacalix [4] arene derivatives by S... PI or S... S forces are connected by "side by side", the formation of nanotubes deposited along the calixarene ring cavity. From these we can see, the main molecular conformation of the molecular determinants is not whether nanotubes, appropriate groups were introduced into the backbone, and in the crystallization environment suitable to the appropriate arrangement the nanotubes are formed by intermolecular interactions. The fourth chapter studies the calixarene strong hydrogen bond acceptor edge exist, respectively with pyridine / methanol and tetrahydrofuran / methanol as solvent, calix [4] arene carboxylic acid derivatives with different conformation (carboxylic acid number = 2). The self-assembly behavior of Calix [4] arene carboxylic acid derivatives cone the conformation of carboxyl in calixarene on the same side, can form hydrogen bonds with other different types of host molecules and solvent molecules; when the same side connected with carboxyl phenyl ring to the ring cavity The contraction (dihedral angle less than 30 degrees, calixarene molecules tend to form by the two to a two mer carboxyl hydrogen bond structure, even when the carboxyl benzene ring to ring expansion body adjacent molecules formed by a pair of carboxyl hydrogen bonds between a one-dimensional wave structure. Some cone and 1,3- alternate conformation calix [4] arene carboxylic acid derivatives, carboxyl on both sides, either directly or in a solvent with the help of forming a one-dimensional wave shaped or chain structure. The solvent molecules on the self-assembly behavior is influenced by pyridine easily through O-H... N hydrogen bonds formed "head to head" two dimeric structure, dominant molecular self-assembly; tetrahydrofuran is a manifestation of help, void filling formed in the crystal; in the absence of strong hydrogen bonding points, methanol can be used as a supplement to the main intermolecular hydrogen bonding site and to "head right" or "side by side" is connected. The fifth chapter studies did not grant strong hydrogen bond receptor and S sulfur atoms exist, the self-assembly behavior of Calix [4] arene derivatives with different conformations. The supramolecular interaction points less, calixarene interaction in intermolecular weak, such as C-H... O, C-H... PI and O... PI, by way of inter molecular close packing of the assistance of forming supramolecular network structure. The steric effect of substituents will affect the lower edge of Calix [4] arene derivatives have different self-assembly behaviors. The present margin of no substituent, aldehyde calix [4] arene cone conformation easy to splice form classification of nanotubes; replace the edge of the base for large flexible propyl, 1,3- alternate conformation of Calix [4] arene four aldehyde molecules in order to effectively reduce the repulsive force between adjacent molecules, molecules in the 90 degree rotation, the formation of three-dimensional C-H through two mutually orthogonal sets of aldehyde... O hydrogen bonds along the molecular ring cavity accumulated to form one-dimensional nano channel; substituent present margin for large steric effect of isopropyl, aldehyde 1,3- alternate conformation of Calix [4] arene derivatives to aldehyde ring cavity contraction molecules through close packed into a three-dimensional structure; in the [4] cup on the edge of the introduction of aromatic hydrocarbons or the lower edge of the introduction of cyano benzoyl can provide different types of supramolecular interactions, assist in the generation of calixarene aggregates.

【學(xué)位授予單位】：武漢大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：O625;TB383.1

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本文編號：1399115