水溶性季吡啶卟啉盐的制备及其电致变色性能研究

Preparation and electrochromic properties of water-soluble quaternary pyridinium porphyrin

采用丙酸回流法制备了四(4-吡啶基)卟啉(TPyP),通过季铵化反应改性TPyP合成水溶性季吡啶卟啉盐(TEPyP^(4+)-Br),并采用一体化工艺制备TPyP和TEPyP^(4+)-Br的电致变色器件。采用核磁共振氢谱(1H-NMR)、傅里叶变换红外光谱(FT-IR)和紫外-可见光谱(UV-Vis)表征化合物的结构;采用密度泛函理论(DFT)计算和循环伏安法(CV)揭示化合物的电子结构与电化学性能;采用原位光谱法和计时电流法(CA)表征器件的电致变色性能。结果表明,TEPyP^(4+)-Br器件能够发生可逆的颜色变化(翠绿色/深绿色),且TEPyP^(4+)-Br器件CA循环100次后的电流密度为84%,相比于未季铵化改性的TPyP(34%)得到较大提升,表明季铵化改性对循环稳定性的调控有效。

Tetra(4-pyridyl)porphyrin(TPyP)was prepared by reflux of propionic acid,and water-soluble quaternary pyridinium porphyrin(TEPyP^(4+)-Br)was synthesized by quaternization of TPyP.The electrochromic devices of TPyP and TEPyP^(4+)-Br were prepared by integrated process.The structures of the compounds were characterized by 1H-NMR,FT-IR and UV-Vis.Density functional theory(DFT)calculations and cyclic voltammetry(CV)were used to reveal the electronic structure and electrochemical properties of the compounds.The electrochromic properties of the devices were characterized by in situ spectroscopy and chronoamperometry(CA).The results showed that the device of TEPyP^(4+)-Br could undergo reversible color change(emerald green/dark green),and the current density after 100 cycles was 84%,which was greatly improved compared with that of the unquaternized TPyP(34%),indicating that quaternization was effective in regulating the cycle stability.