Study of Synthesis and Physical Properties of New Electron Donor Compounds Incorporating Ferrocene Moiety as New Conductors

寻找新的电活性材料是当今化学家非常活跃的研究课题。近年来，合成新的π-扩展给体已成为许多化学家感兴趣的领域。合成了一系列由含二茂铁的共轭间隔基隔开的π-延伸共轭四硫富瓦烯（TTF）类似物作为新的π-给体，并通过实验技术和光谱分析对其结构和物理性质进行了表征。研究了π-扩展二茂铁基给体的紫外-可见光谱和循环伏安特性，并与二茂铁、二茂铁醌进行了比较。观察到三电子氧化还原行为为单波。同时，还报道了一条合成四硫富瓦烯二甲酯（TTF-DME）的简单路线。通过引入酯配位官能团作为双官能团给体，合成了四硫富瓦烯二甲酯TTF-DME。通过循环伏安法研究了TTF-DME的氧化还原行为，并与公知的DB-TTF进行了比较。此外，本课题的目的是合成二茂铁酮类化合物，并以此作为Wittig-Horner反应的起点。用上述方法合成了二茂铁基酮，并与1，3-苯并二硫杂环戊烯-2-膦酸酯在正丁基锂存在下，于-78 ℃，无水THF中反应，得到相应的二茂铁-二硫富瓦烯（Fc-DTF's）和二茂铁-四硫富瓦烯（Fc-TTF's）。用紫外-可见光谱和循环伏安法研究了新给体化合物的电化学性质。研究了新化合物的循环伏安法和吸收光谱，并与二茂铁和二苯并四硫富瓦烯进行了比较。观察到二电子和三电子氧化还原行为为双波。

The search for new electro active materials is nowadays very active field of research topic for chemists. Recently, the synthesis of new π-extended donors has become a great area of interest for many chemists. A number of π-extended conjugated tetrathiafulvalen (TTF) analogues separated by a conjugated spacer incorporating ferrocene moiety were successively synthesized as new π-donors and their structure and physical properties were characterized both by experimental techniques and spectral analysis. UV-Vis spectra and cyclic voltammetry of the π-extended ferrocenyl donor were studied in comparison with ferrocene, and ferrocenylquinone. A three-electron redox behavior was observed as a single wave. The absorption spectrum showed a slight red-shift and slight increase in the intensity.On the other hand, a simple route for synthesis of new tetrathiafulvalene dimethyl ester (TTF-DME) is reported. The tetrathifulvalene dimethylester TTF-DME has been prepared by introducing an ester coordination function as a bifunctional new donor. The redox behavior of the TTF-DME was investigated in comparison to the well-known DB-TTF by cyclic voltammetry. A two-electron redox behavior was observed as a two waves.Moreover, the synthesis of ferrocenylketone compounds and conducted to be a starting for the Wittig-Horner reaction is the aim of our topic. The ferrocenylketones have been synthesized via described methods, and allowed to react with l,3-benzodithiole-2-phosphonate ester in the presence of n-BuLi at - 78℃ in dry THF to afford the corresponding ferrocene-dithiafulvalenes (Fc-DTF's) and ferrocene-tetrathiafulvalene (Fc-TTF). Electrochemical properties of the new donor compounds were studied using UV-Vis spectra and cyclic voltamogram spectrophotometer (CV). Cyclic voltammetry (CV) and absorption spectra of the new compounds were studied in comparison with ferrocene and dibenzo-tetrathiafulvalene. A two-electron and three-electron redox behavior was observed as a two waves.