间苯二甲醛缩双芳氨基硫脲的合成及阴离子识别研究

设计合成了5种间苯二甲醛缩双芳氨基硫脲受体分子, 利用紫外-可见吸收光谱及1H NMR, 考察了其与F-, Cl-, Br-, I-, CH3COO-, HSO-4, NO-3和H2PO-4等8种阴离子的作用. 当在受体分子S0, S1, S2, S3和S4的DMSO溶液中加入F-和CH3COO-四丁基铵盐的DMSO溶液时, 吸收光谱发生显著红移, 溶液颜色由无色变为深黄色, 而加入其它阴离子则无显著变化, 可以实现对这两种阴离子的裸眼检测及光谱分析. 计算结果表明, 随着苯环上取代基的变化, 此5种受体分子对F-和CH3COO-的识别作用呈现规律性变化. 1H NMR 及质子溶剂效应进一步证明了受体分子与阴离子之间以氢键作用方式相结合. Job工作曲线表明, 该类受体分子与阴离子形成1∶1的氢键配合物.

Synthesis of Isophthalic Aldehyde Bis-arylthiosemicarbazone and Their Anion Recognition Properties

Five new isophthalic aldehyde bis-arylthiosemicarbazone receptors were designed and synthesized. The binding properties of the receptors with anions such as F-, Cl-, Br-, I-, CH3COO-, HSO-4 , H2PO-4 and NO-3 in DMSO were investigated byUV-Vis and 1H NMR spectroscopy. A clear color change was observed from colorless to deep yellow upon addition of F- and CH3COO- to the solution of the five receptors in DMSO. The results show that the five receptors had a better selectivity of F- and CH3COO-, but had no evident binding with Cl-, Br-, I-, HSO-4, H2PO-4 and NO-3. It was regular that the five receptors had different binding abilities with F- and CH3COO-. The UV-Vis data indicate that a 1∶1 stoichiometry complex was formed between the receptors and the two anions. 1H NMR titrations and solvation effect confirmed hydrogen bonding interaction between the receptors and anions.