五元杂环spacer结构调控的分子内电荷交互作用

研究五元杂环(spacer)桥对分子内电荷传递调控规律是开发功能分子材料的基础。本文通过环合反应制备了9个2,5-双二茂铁基五元杂环衍生物,包括: 2,5-双二茂铁基-1-苯基-吡咯(1),2,5-双二茂铁基呋喃(2),2,5-双二茂铁基噻吩(3),2,5-双二茂铁基-1H-咪唑(4),2,5-双二茂铁基噁唑(5),2,5-双二茂铁基噻唑(6),2,5-双二茂铁基-1H-1,3,4-三氮唑(7),2,5-双二茂铁基-1,3,4-噁二唑(8)和2,5-双二茂铁基-1,3,4-噻二唑(9)作为模型分子。通过元素分析,傅里叶变换红外(FTIR)光谱,质谱(MS)和核磁共振(NMR)等手段对化合物结构进行了表征,采用循环伏安电化学(CV)和密度泛函(DFT)量化模拟计算研究了分子内电荷传递与五元杂环(spacer)结构间的调控关系,发现化合物(1-9)二茂铁间电荷交互作用随着spacer中杂原子数量的增加而减小,分子内电荷选择短程杂原子桥作为传输通道,spacer结构对二茂铁间电荷传递发挥着重要的调控作用。

The intramolecular electronic interaction regulated by five-membered heterocycle spacer structure

The study of the intramolecular electronic interaction of five-membered heterocycle (spacer) is the basis of developing functional molecular materials. In this work, nine 2,5-diferrocenyl five-membered heterocyclic molecules are synthesized as models to investigate the effect of intramolecular electron-transfer properties systematically, including 2,5-diferrocenyl-1-phenyl-pyrrole (1), 2,5-diferrocenylfuran (2), 2,5-diferrocenylthiophene (3), 2,5-diferrocenyl-1H-imidazole (4), 2,5-diferrocenyloxazole (5), 2,5-diferrocenylthiazole (6), 2,5-diferrocenyl-1H-1,3,4-triazole (7), 2,5-diferrocenyl-1,3,4-oxadiazole (8) and 2,5-diferrocenyl-1,3,4-thiadiazole (9). The molecules characterized by Elemental analysis, FT-IR, MS and NMR. The intramolecular electronic interactions regulated by spacer structure investigated through cyclic voltammetry in combination with density functional theory (DFT) calculations. The results revealed that the electronic interaction of molecules (1-9) decreased with the increase of heteroatoms in central heterocycle spacer; the intramolecular electronic interaction selects the short-range heteroatomic bridge as the transport channel and the electron-transfer property can be regulated by central heterocycle spacer structure.