【摘要】：卟啉是一類具有四個吡咯通過次甲基橋相連的共軛大環(huán)化合物,它們在醫(yī)學(xué)和材料化學(xué)等領(lǐng)域都有著廣泛的應(yīng)用前景。六元卟啉則是具有六個吡咯相連的拓展大環(huán)化合物,它們具有更為獨特的光化學(xué)和電化學(xué)性質(zhì),因此對這些化合物進(jìn)行研究具有重要的學(xué)術(shù)意義和潛在的應(yīng)用價值。本論文第一章綜述了卟啉及拓展卟啉的結(jié)構(gòu)特性、在醫(yī)學(xué)和材料等方面的應(yīng)用以及采用的研究方法。第二章研究了三種無金屬卟啉在不同溶劑中的電化學(xué)性質(zhì),討論了溶劑對氧化還原反應(yīng)的影響。每一種化合物在給定溶劑中的氧化還原反應(yīng)均為卟啉大環(huán)上的電子轉(zhuǎn)移過程,第一級還原反應(yīng)的產(chǎn)物為卟啉陰離子自由基,而第一級氧化反應(yīng)的產(chǎn)物為卟啉陽離子自由基。另外,還研究了HexaPyH_2在二氯甲烷中的質(zhì)子化反應(yīng),與三氟乙酸反應(yīng)時,HexaPyH_2可以一步得到兩個質(zhì)子生成[HexaPyH_4]~(2+)。第三章研究了兩種常規(guī)銅、鋅卟啉以及兩種六元銅、鋅卟啉在非水溶劑中的電化學(xué)和光譜電化學(xué)性質(zhì)。結(jié)果表明,常規(guī)的銅、鋅卟啉在給定的溶劑中均可以發(fā)生兩級一電子還原反應(yīng),生成負(fù)一價陰離子[T2,6-diFPPM]~-和負(fù)二價陰離子[T2,6-diFPPM]~(2-)。但是在相同的溶劑中,六元卟啉銅、鋅均能發(fā)生四級可逆的一電子還原反應(yīng),生成負(fù)一到負(fù)四價的卟啉陰離子,即:[HexaPyM_2]~-,[HexaPyM_2]~(2-),[HexaPyM_2]~(3-)和[HexaPyM_2]~(4-)。第四章研究了T2,6-diFPPCo和HexaPyCo_2在非水溶劑中的電化學(xué)和光譜電化學(xué)性質(zhì)。在二氯甲烷或苯腈中,T2,6-diFPPCo的第一級還原和第一級氧化反應(yīng)均為金屬中心的電子轉(zhuǎn)移過程,其中還原反應(yīng)的產(chǎn)物為Co(Ⅰ)卟啉,而氧化反應(yīng)產(chǎn)物為Co(Ⅲ)卟啉。對于含有兩個鈷中心離子的六元卟啉HexaPyCo_2來說,在同樣的溶劑中可以觀察到三級還原反應(yīng),其中第一、二兩級還原為分子中兩個Co(Ⅱ)離子分別得到一個電子被還原為Co(Ⅰ)卟啉。六元鈷卟啉的前兩級氧化反應(yīng)也都是金屬中心的電子轉(zhuǎn)移過程,分子中兩個Co(Ⅱ)離子分別失去一個電子最終生成含有兩個三價鈷中心離子的正二價卟啉陽離子,[HexaPyCo_2~Ⅲ]~(2+)。在吡啶中,六元卟啉鈷能夠與吡啶發(fā)生軸向配位反應(yīng)生成五配位的化合物,每一個鈷離子會配位一個吡啶而生成[HexaPyCo_2(py)_2]。[HexaPyCo_2(py)_2]在吡啶中可以觀察到三級還原反應(yīng),其中第一級是兩個重迭的一電子還原過程,生成的產(chǎn)物為含有兩個Co(Ⅰ)的六元卟啉。在第四章中還研究了T2,6-diFPPCo和HexaPyCo_2與咪唑、甲基咪唑、吡啶、甲基吡啶在二氯甲烷中的軸向配位反應(yīng),測定了相應(yīng)的配位反應(yīng)平衡常數(shù)。另外,采用旋轉(zhuǎn)盤電極技術(shù)研究了六元卟啉鈷在水溶液中催化還原氧氣的性能,結(jié)果表明,在1.0 M HClO_4中,HexaPyCo_2可以用作氧氣還原的電催化劑,在給定的實驗條件下,氧氣的還原反應(yīng)為兩電子過程,產(chǎn)物主要是過氧化氫。
[Abstract]:Porphyrins are a class of conjugated macrocyclic compounds with four pyrrole linked by methylene bridge. They have been widely used in medicine and material chemistry. Hexagonal porphyrins are extended macrocyclic compounds with six pyrrole links, which have more unique photochemical and electrochemical properties. Therefore, the study of these compounds has important academic significance and potential application value. In the first chapter of this paper, the structural properties of porphyrins and their applications in medicine and materials, as well as their research methods are reviewed. In chapter 2, the electrochemical properties of three metalloporphyrins in different solvents were studied, and the effects of solvents on the redox reaction were discussed. The redox reaction of each compound in a given solvent is an electron transfer process over a porphyrin macroring. The product of the first order reduction reaction is a porphyrin anion radical, while the first order oxidation reaction product is a porphyrin cationic radical. In addition, the proton reaction of HexaPyH_2 in dichloromethane was studied. In the reaction of HexaPyH_2 with trifluoroacetic acid, two protons [HexaPyH_4] ~ (2) were obtained in one step. In chapter 3, the electrochemical and spectral electrochemical properties of two kinds of conventional copper, zinc porphyrin and two kinds of hexagonal copper and zinc porphyrin in non-aqueous solvent were studied. The results show that conventional copper and zinc porphyrins can undergo two-stage one-order electron reduction reaction in a given solvent to produce negative monovalent anions [T2O6-diFPPM] ~-and negative divalent anions [T2O6-diFPPM] ~ (2-). However, in the same solvent, hexagonal porphyrin copper and zinc can undergo a fourth order reversible electron reduction reaction to form negative 1 to negative tetravalent porphyrin anions, that is, [HexaPyM_2] ~ -, [HexaPyM_2] ~ (2-), [HexaPyM_2] ~ (3-) and [HexaPyM_2] ~ (4-). In chapter 4, the electrochemical and spectral electrochemical properties of T2O6-diFPPCo and HexaPyCo_2 in non-aqueous solvents were studied. In dichloromethane or benzonitrile, the first stage reduction and the first order oxidation of T2N 6-diFPPCo are electron transfer processes of the metal center, in which the product of reduction reaction is Co (鈪，

本文編號：2289987