本文選題：二茂鐵 + 六元芳環(huán)��； 參考：《內(nèi)蒙古工業(yè)大學》2017年碩士論文

【摘要】：由于二茂鐵衍生物在電化學領(lǐng)域表現(xiàn)出良好的氧化還原特性,很多研究者在二茂鐵功能化分子的構(gòu)建和電化學性質(zhì)研究方面進行了探索,特別是在二茂鐵單元間電荷傳遞通道和影響因素等方面開展了大量工作,并且總結(jié)出二茂鐵單元間的電子交互主要受橋的類型、橋原子種類、氧化還原中心的空間距離、取代基誘導效應(yīng)、橋電荷密度、分子拓撲結(jié)構(gòu)以及支持電解質(zhì)種類等因素的影響。在前期關(guān)于二茂鐵模型化合物電子傳遞性能研究當中,人們在各種原子橋、共軛和非共軛線型橋、共軛五元雜環(huán)橋以及苯基橋聯(lián)的二茂鐵化合物進行了大量的研究工作,而對于以六元雜環(huán)為橋的多二茂鐵化合物電化學傳遞特性的研究報道甚少。本文采用Negishi偶聯(lián)反應(yīng)成功合成了六種二茂鐵基取代吡啶、嘧啶和三嗪化合物,并結(jié)合結(jié)構(gòu)、紫外光譜、理論計算對其循環(huán)伏安性質(zhì)進行了研究。1、二茂鐵基取代吡啶、嘧啶和三嗪的合成論文采用新制備的二茂鐵基氯化鋅,在[1,1'-雙(二苯基膦基)二茂鐵]二氯化鈀[Pd(dppf)Cl2]催化下,分別與不同當量的2,4,6-三溴吡啶、2,4,6-三氯-1,3-嘧啶、2,4,6-三氯-1,3,5-三嗪發(fā)生Negishi偶聯(lián)反應(yīng),合成了三種二茂鐵基取代吡啶、嘧啶和三嗪化合物:2-溴-4,6-雙二茂鐵基吡啶(1)、2-氯-4,6-雙二茂鐵基-1,3-嘧啶(2)、2-氯-4,6-雙二茂鐵基-1,3,5-三嗪(3);三種三二茂鐵基取代吡啶、嘧啶和三嗪化合物:2,4,6-三二茂鐵基吡啶(4)、2,4,6-三二茂鐵基-1,3-嘧啶(5)、2,4,6-三二茂鐵基-1,3,5-三嗪(6)。論文采用元素分析、紅外光譜、質(zhì)譜、核磁共振、紫外光譜等對化合物的組成和結(jié)構(gòu)進行了表征,并通過X-射線單晶衍射確定了化合物3、4、6的分子與晶體結(jié)構(gòu)。化合物1、2、3、5為首次合成的4個新化合物;化合物3和6為首次報道的新型分子晶體結(jié)構(gòu)。2、電化學性質(zhì)研究論文采用循環(huán)伏安法對六種化合物進行了電化學測試,同時結(jié)合理論計算、晶體結(jié)構(gòu)對化合物中二茂鐵單元間電子交互通道和影響電子交互的因素進行了分析。研究結(jié)果表明:雙二茂鐵基吡啶、嘧啶、三嗪三個化合物中二茂鐵單元間的電荷傳遞不是通過最短的橋,而是通過π共軛橋而發(fā)生作用的,同時隨著π共軛橋的電荷密度減小,二茂鐵單元間的電子交互作用逐漸減小,并且隨著中心環(huán)氮原子數(shù)的增多,體系的共軛性逐漸增強,導致對二茂鐵單元電荷的分散作用加大,使得首個氧化峰電位向高電位偏移;三二茂鐵基吡啶、嘧啶、三嗪三個化合物中二茂鐵單元的電子交互作用也是隨著π共軛橋的電荷密度減小而逐漸減小的,同時三者的第一氧化峰電位隨著HOMO軌道能量的降低而依次升高。
[Abstract]:Because ferrocene derivatives exhibit good redox properties in the electrochemical field, many researchers have explored the construction of ferrocene functionalized molecules and the study of electrochemical properties. In particular, a great deal of work has been done in charge transfer channels and influencing factors among ferrocene units, and it is concluded that the electronic interaction between ferrocene units is mainly affected by the type of bridge, the type of bridge atoms, the space distance of redox centers, and so on. The effects of substituent inductive effect, bridge charge density, molecular topological structure and kinds of supporting electrolytes. In previous studies on the electron transport properties of ferrocene model compounds, a great deal of work has been done on various atomic bridges, conjugated and unconjugated linear bridges, conjugated five-element heterocyclic bridges and phenyl bridged ferrocene compounds. However, there are few reports on the electrochemical transport properties of polyferrocene compounds with hexahedral heterocycles as the bridge. In this paper, six ferrocenyl substituted pyridine, pyrimidine and triazine compounds were successfully synthesized by Negishi coupling reaction. The synthesis of pyrimidine and triazine was studied by using newly prepared ferrocenyl zinc chloride under the catalysis of [1 (1) -bis (diphenylphosphine) ferrocene] palladium [Pd(dppf)Cl2]. Three kinds of ferrocenyl substituted pyridine were synthesized by Negishi coupling reaction with different equivalent 2H 4N 6- trichloropyridine-6-trichloro-6-trichloro-3-pyrimidine, respectively, in which three ferrocenyl pyridine substituted pyridines were synthesized. Pyrimidine and triazine compounds: 2-bromo-6-diferrocenylpyridine, 2-chloro-4-diferrocenyl, 6-diferrocenyl, 2-pyrimidine, 2-chloro-4-diferrocenyl, 6-diferrocenyl, 5-triazinone; three kinds of ferrocenyl substituted pyridine, Pyrimidine and triazine compounds 2: 4, 4, 6-triferrocenyl pyridine, 2, 2, 6-triferrocenyl-1, 1, 3-pyrimidine, 2, 4, 6-triferrocenyl, 3-1, 3-triazinyl, 6-triferrocenyl, 5-triazinyl, 6-triferrocenyl, 6-triferrocenylpyridine. The composition and structure of the compound were characterized by elemental analysis, IR, MS, NMR and UV spectra, and the molecular and crystal structure of compound 3O4N6 was determined by X-ray single crystal diffraction. Compounds 1, 2, O, 3 and 5 are four new compounds synthesized for the first time, and compounds 3 and 6 are new molecular crystal structures reported for the first time. The electrochemical properties of these compounds have been measured by cyclic voltammetry. At the same time, the crystal structure was used to analyze the electronic interaction channel between ferrocene units and the factors affecting the electronic interaction. The results show that the charge transfer between ferrocene units in three compounds, pyridine, pyrimidine and triazine, occurs not by the shortest bridge, but by 蟺 conjugate bridge, and decreases with the decrease of the charge density of 蟺 conjugate bridge. The electron interaction between ferrocene units decreases gradually, and with the increase of the number of central ring nitrogen atoms, the conjugation of the system increases gradually, which leads to the dispersion of the charge of ferrocene units. The electron interaction of ferrocene units in ferrocene pyridine, pyrimidine and triazine compounds decreases with the decrease of the charge density of 蟺 conjugate bridge. At the same time, the first oxidation peak potential of the three increases with the decrease of HOMO orbital energy.
【學位授予單位】：內(nèi)蒙古工業(yè)大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O627.81

【參考文獻】

中國期刊全文數(shù)據(jù)庫 前1條

1 劉萬毅,袁耀鋒,張凌云,王積濤;烷基橋聯(lián)雙二茂鐵衍生物的取代基效應(yīng)與電化學性質(zhì)的研究[J];高等學�；瘜W學報;1998年08期

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本文編號：1926563