基于萘-咟啶鎓受体分子的合成及其对F-的特性识别

设计合成了基于萘-咟啶鎓的受体分子1,通过紫外-可见光谱、荧光光谱研究了受体分子1对9种常见的阴离子(F^-、 Cl^-、 Br^-、 I^-、 CH₃COO^-、 HSO^-₄、 H₂PO^-₄、 ClO^-₄、 NO^-₃)的识别性能.结果发现,受体分子1可选择性的识别F^-.在紫外-可见光谱中,当加入F^-时,受体分子1的溶液由黄色变为无色,可实现裸眼识别,Job^-曲线表明受体分子1和F^-形成了1∶1型氢键络合物,结合常数为(3.05±0.15)×10³ L/mol. 在荧光光谱中,加入F^-后,受体分子1在403 nm处产生强的荧光发射峰,由无荧光变为深蓝色荧光,即具有荧光开启(turn-on)功效,受体分子1检测F^-的线性为1.0×10^-6~3.0×10^-5 mol/L,最低检测限为8.5×10^-6 mol/L. 核磁滴定实验表明受体分子1通过咟啶环上的C(2)-H与F^-之间形成了较强的氢键作用力,而过量F^-的加入会引起受体分子的去质子化.

Synthesis of naphthyl-perimidium based receptor and selective recognition of fluoride

A novel naphthyl-perimidium based receptor 1 was synthesized. The interaction between receptor 1 and nine common anions(F^-, Cl^-, Br^-, I^-, CH₃COO^-, HSO^-₄, H₂PO₄^-, ClO₄^-, NO^-₃)were studied by UV-Vis and FL spectroscopies. The results indicated that receptor 1 should selective recognition of F^-. In UV-Vis spectra, When F^- was added, the color of receptor 1 solution changed from yellow to colorless, the results indicated that 1 could behave as a colorimetric chemosensor for F^-. Job plot demonstrated that receptor 1 formed 1∶1 complex with F^-, and the binding constant is(3.05±0.15)×10³ L/mol. In fluorescent spectra, the non-fluorescent solution of 1 exhibited strong blue fluorescence when F^- was added, and a strong emission peak at 403 nm was found with the turn-on effect. The detection linear range for F^- was 1.0×10^-6—3.0×10^-5 mol/L, and the detection limit was 8.5×10^-6 mol/L. The ¹H NMR investigation confirmed that the hydrogen bond was formed between F^- and the C(2)-H of receptor 1, the excessive of F^- will cause deprotonation of receptor 1.