超分子聚合物論文芳脒類超分子和氮雜β-二亞胺化合物的合成及碳氮鍵裂分機(jī)理的研究

1、 超分子聚合物論文：芳脒類超分子和氮雜-二亞胺化合物的合成及碳氮鍵裂分機(jī)理的研究【中文摘要】在社會發(fā)展的過程中,隨著人們對各種材料性能需求的不斷提升及其有關(guān)化學(xué)新現(xiàn)象的呈現(xiàn),推動著材料化學(xué)理論與應(yīng)用的研究不斷向著更高的層次深入。利用超分子化學(xué)體系的理論設(shè)計(jì)合成的功能性材料,因其性能獨(dú)特且優(yōu)良實(shí)用的特征滿足了社會的需求,同時(shí)解決了人們在化學(xué)發(fā)展中的新問題,成為了21世紀(jì)科技發(fā)展的重點(diǎn)領(lǐng)域之一。作為該領(lǐng)域的重要分支,近些年來離子型超分子聚合結(jié)構(gòu)材料和有機(jī)金屬配合物的研究發(fā)展的很快。本文設(shè)計(jì)合成了一些芳脒基碳正離子和不同的負(fù)離子結(jié)合生成的離子型超分子聚合物,以及與其相關(guān)的有機(jī)化合物,在測定其結(jié)構(gòu)的基

2、礎(chǔ)上,檢測了部分化合物的熒光性能。論文的研究工作建立在課題組以往的理論和實(shí)驗(yàn)的基礎(chǔ)上,設(shè)計(jì)了芳基腈和不同的烷基胺基鋰鹽進(jìn)行反應(yīng),得到了10個(gè)化合物,用X-ray單晶衍射分析測定了化合物2a,2b,2c,2d,3a,3b的結(jié)構(gòu),并用NMR、IR、ESI-MS進(jìn)行了詳細(xì)的表征。對化合物2e,2f,2g,2h進(jìn)行了ESI-MS分析。論文主要可分為四部分。第一部分：概括介紹了超分子化學(xué)和功能性材料的理論以及國內(nèi)外研究發(fā)展?fàn)顩r,介紹了碳氮鍵的裂分反應(yīng)和當(dāng)前的研究進(jìn)展。第二部分：以2-甲基苯基腈、4-吡啶腈、2-硝基苯腈、苯甲腈為原料、與不同的烷基胺鋰進(jìn)行加成反應(yīng),在此基礎(chǔ)上與金屬氯化鹽或一氯化二苯基膦進(jìn)

3、行置換反應(yīng),接著用雙氧水氧化,合成了6個(gè)化合物2a,2b,2c,2d,2e,2f,2g,2h其中2a,2c為芳脒類離子型超分子,2b,2d為有機(jī)化合物。通過表征發(fā)現(xiàn)在形成化合物2a；2b,2c的過程中,有碳氮鍵裂分的現(xiàn)象。為探討這一現(xiàn)象的原因,合成并分析了四種化合物2e,2f,2g,2h,對反應(yīng)過程中所發(fā)生的碳氮鍵的裂分反應(yīng)進(jìn)行了著重的闡述和推測。對芳脒類離子型超分子2a,2c進(jìn)行了熒光性質(zhì)分析。第三部分：以4-吡啶腈,4-硝基苯甲腈與不同的烷基胺鋰反應(yīng)后,再與一氯二苯基膦反應(yīng),暴露在空氣中氧化得到了氮雜p-二亞胺離子型超分子聚合物3a,進(jìn)一步證明了氮雜-二亞胺是可以穩(wěn)定存在的骨架；用雙氧水氧

4、化得到了N-P鍵未發(fā)生氧化裂分的氮雜p-二亞胺化合物,并對化合物3a,3b進(jìn)行了結(jié)構(gòu)測定和詳細(xì)表征,探討了其生成的機(jī)理。第四部分：通過對前三部分的回顧總結(jié),在分析有關(guān)碳氮鍵的裂分機(jī)理的基礎(chǔ)上,設(shè)計(jì)了氧化劑影響氮磷鍵和碳氮鍵裂分反應(yīng)的驗(yàn)證方法。展望了合成更好的芳脒基類離子型超分子熒光材料和氮雜-二亞胺與金屬離子配位所生成的化合物在催化領(lǐng)域的潛在價(jià)值?；衔?a,2b,2c,2d,3a,3b的結(jié)構(gòu),經(jīng)NMR、IR、ESI-MS和X-ray單晶衍射確證?；衔?e,2f,2g,2h經(jīng)ESI-MS檢測。其中,2a,2c,3a,3b這4種化合物為未見文獻(xiàn)報(bào)道的新化合物?！居⑽恼縄n the proc

5、ess of human development, the theoretical research and application of material science towards a higher horizontal by the increasing needs to various of material properties and the appearance of new chemical phenomena. The functional materials based on the principle of supramolecular chemistry becau

6、se of its unique characteristics of high performance meet the practical needs, which solves the new problems in chemical development and is one of the important of science and technology in 21st century. Ionic supramolecular polymeric structure material and organic metal complexes, as one of the bra

7、nch, were developed quickly in recent years. In the thesis, we designed and synthesized several charge assisted hydrogen bond supramolecular polymeric compounds composed by benzamidine carbocation with various of anions. Structural characterization and fluorescence properties of them were determined

8、.Ten compounds by reacting-hydrogen-free aryl nitriles with different alkyl amino lithium have been prepared. The molecular structures of compounds 2a,2c, 2d,2b,3a were determined by X-ray crystallography and confirmed by IR, NMR ESI-MS. Compounds 2e,2f,2g,2h were examined by ESI-MS. The main conten

9、ts are divided into four sections.Part I:The latest development of supramolecular chemistry and functional materials was introduced. Whats more, the recent development of cleavage reaction about carbon nitrogen bonds was given.Part II:The compounds of 2a,2b,2c,2d,2e,2f,2g,2h were synthesized by trea

10、tment of R2NLi(R=Me,Et) witha-hydrogen-free aryl nitriles, followed the metatheses of chlorodiphenylphosphine or metal chlorides and oxidizing by hydrogen peroxide,2a,2c belongs to benzamidine Ionic supramolecular polymerization,2b,2d were organic compounds. The cleavage phenomenon about C-N bond wa

11、s found and the mechanism was proposed by the synthesis 2e,2f,2g and 2h. The fluorescence properties of 2a,2c were measured.Part III:Two aza-diimine compounds have been prepared by 4-cyanopyridine and 4-nitrobenzonitrile reacting with R.2NLi(R=Me,Et) and chlorodiphenylphosphine. Aza-diimine charge a

12、ssisted hydrogen bond supramolecular polymeric compound 3a was synthesized by exposing in air,while N-P bond cleavage reaction have been not observed in the 3b.The results demonstrated that aza-diimine was a stable skeleton and compounds structure were detailed characterized by X-ray crystallography

13、, IR, NMR,ESI-MS.Part IV:The contents of research were summarized. The experimental design about the influence of oxidant in C-N bond cleavage process was submitted. The application of these compounds in materials chemistry was viewed.【關(guān)鍵詞】超分子聚合物 碳氮鍵裂分 晶體結(jié)構(gòu) 氮雜-二亞胺【英文關(guān)鍵詞】supramolecular polymer C-N bo

14、nd cleavage Crystal structure Aza-diimine【目錄】芳脒類超分子和氮雜-二亞胺化合物的合成及碳氮鍵裂分機(jī)理的研究摘要4-6Abstract6-7第一章 緒論10-321.1 超分子化學(xué)體系的起源10-161.1.1 超分子化學(xué)的定義及分子間作用力11-121.1.2 超分子化學(xué)中的分子識別和自組裝12-151.1.3 晶體工程15-161.2 功能性超分子材料16-251.2.1 超分子材料概述16-181.2.2 超分子聚合物18-231.2.3 目前國內(nèi)外超分子材料的研究動態(tài)23-251.3 碳氮鍵裂分的探討及其應(yīng)用25-271.3.1 人名反應(yīng)中的碳

15、氮鍵裂分現(xiàn)象25-261.3.2 過渡金屬絡(luò)合物引發(fā)的碳氮鍵裂分反應(yīng)261.3.3 其他類型的碳氮鍵裂分261.3.4 碳氮鍵裂分的應(yīng)用26-271.4 本實(shí)驗(yàn)的研究進(jìn)展27參考文獻(xiàn)27-32第二章 芳脒類超分子聚合物的合成、表征及相關(guān)碳氮鍵裂分機(jī)理的推測32-552.1 超分子聚合物及相關(guān)有機(jī)物的合成33-372.1.1 化合物2a,2b,2c,2d,2e,2f,2g,2h的合成33-372.2 結(jié)果與討論37-502.2.1 化合物2a,2b,2c,2d,2e,2f,2g,2h的表征與分析37-442.2.2 化合物2a,2c的熒光性質(zhì)44-472.2.3 化合物2a,2b,2c的反應(yīng)機(jī)理47-502