有机化学 ›› 2017, Vol. 37 ›› Issue (9): 2328-2335.DOI: 10.6023/cjoc201703049 上一篇    下一篇

研究论文

单取代与1,1'-双取代1,2,3-三唑基二茂铁衍生物的光谱、电化学与热性质

钱超, 绰洛鹏, 赵海英, 边占喜   

  1. 内蒙古大学化学化工学院 内蒙古自治区精细有机合成重点实验室 呼和浩特 010021
  • 收稿日期:2017-03-29 修回日期:2017-04-27 出版日期:2017-09-25 发布日期:2017-05-17
  • 通讯作者: 赵海英 E-mail:hyzhao@imu.edu.cn
  • 基金资助:

    国家自然科学基金(No.21562032)、内蒙古自治区高等学校科学研究(No.NJZZ001)和内蒙古自治区自然科学基金(No.2013MS0207)资助项目.

Spectroscopic, Electrochemistry and Thermal Properties of Monoand 1,1'-Disubstituted 1,2,3-Triazolylferrocene Derivatives

Qian Chao, Chuo Luopeng, Zhao Haiying, Bian Zhanxi   

  1. College of Chemistry and Chemical Engineering, Inner Mongolia University, Inner Mongolia Key Laboratory of Fine Organic Synthesis, Hohhot 010021
  • Received:2017-03-29 Revised:2017-04-27 Online:2017-09-25 Published:2017-05-17
  • Contact: 10.6023/cjoc201703049 E-mail:hyzhao@imu.edu.cn
  • Supported by:

    Project supported by National Natural Science Foundation of China (No. 21562032), the Research Program of Science and Technology at Universities of Inner Mongolia (No. NJZZ001) and the Natural Science Foundation of Inner Mongolia (Nos. 2013MS0207).

合成并表征了一系列单取代及1,1'-双取代1,2,3-三唑基二茂铁衍生物.与单取代二茂铁衍生物相比,1,1'-双取代二茂铁衍生物具有较大的摩尔吸光系数.荧光光谱中,烷氧链的增加和氯原子的引入均使化合物的荧光强度减弱,量子产率降低.循环伏安实验中,代表化合物展示准可逆的单电子氧化还原进程,并且1,1'-双取代三唑基二茂铁衍生物的半波氧化还原电位较单取代化合物向阳极移动150 mV左右,表明前者难于发生失电子氧化反应.热性质研究表明,这些化合物的降解温度在285~305℃之间.含有单烷氧链的单取代二茂铁衍生物熔点较高,在加热过程中未熔解而是直接发生了降解反应;含有多烷氧链的化合物熔点降低,在加热和冷却过程中有的发生了单晶相的熔解和凝固过程,有的发生了多晶相到液相的转变.

关键词: 二茂铁, 三唑, 光谱, 电化学, 热性质

A series of mono-and 1,1'-disubstituted 1,2,3-triazolylferrocene derivatives have been synthesized and characterized. In UV-Vis spectroscopy, 1,1'-disubstituted compounds have the larger molar absorption coefficient than those of monosubstituted compounds. The fluorescence intensity weakened with increasing the number of alkoxy chain and further weakened after introduction of the highly electronegative chlorine atom. All new compounds showed quasireversible redox process. The potentials for 1,1'-disubstituted 1,2,3-triazolylferrocene derivatives anodically shifted about 150 mV compared with those of monosubstituted compounds, indicating harder oxidation by loss of an electron for the former. These compounds started to decompose at about 285~305℃. The 1,2,3-triazolylferrocene derivative with one terminal alkoxy chain had high melting point, and suffered from degradation reaction before changing into isotropic liquid, and those with multiterminal alkoxy chains showed either simple melting and freezing process or crystal polymorphic phase to isotropic liquid phase transitions in the heating and cooling cycles.

Key words: ferrocene, triazole, spectrum, electrochemistry, thermal behavior