氨基硫脲分子钳的合成及对阴离子的识别作用  

Synthesis of Molecular Tweezers Based on Thiosemi-Carbazide and Their Anion Recognition Properties

作　　者：伍家卫[1,2] 唐蓉萍[1] 索陇宁[1] 杨兴锴[1] 魏太保[2] 周艳青[1,2] 

机构地区：[1]兰州石化职业技术学院石油化学工程系,兰州730060 [2]西北师范大学化学化工学院,兰州730070

出　　处：《应用化学》2011年第11期1274-1279,共6页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(20671077);甘肃省省属高校基本科研业务费资助项目甘财教(2009-192)

摘　　要：合成了2个新型氨基硫脲分子钳主体3a(1,3-二(o-甲苯氧乙酰氨基硫脲甲酰基)苯)和3b(1,3-二(p-甲苯氧乙酰氨基硫脲甲酰基)苯),利用UV-Vis和1H NMR测试其对F-、AcO-、Cl-、Br-和I-的阴离子识别性质。结果表明,主体分子在DMSO溶液中对F-和AcO-表现出明显的选择性识别。1H NMR光谱证明,主体分子与阴离子之间以氢键相结合,结合Job曲线得出主体分子与阴离子之间形成1:1型氢键缔合物。讨论了NH识别位点数及空间结构对识别性质的影响。与硫脲对比,主体3a具有多个NH结合位点,可形成多个氢键,结合常数(Ks)更大。与化合物3b相比,主体3a较大的空间位阻阻碍了其与阴离子的结合,因此两种主体分子与F-和AcO-结合常数均体现为Ks(F-)>Ks(AcO-)。Two novel molecular receptors based on thiosemicarbazide,compound 3a（1,3-bis（o-tolueneoxoacetylthio-semicarbazideacyl） benzene） and compound 3b（1,3-bis（p-tolueneoxoacetylthio-semicarbazideacyl）benzene）,have been designed and synthesized under solid-liquid phase transfer catalysis conditions.The binding properties for anions such as F-,AcO-,Cl-,Br-and I-in DMSO have been examined by UV-Vis and 1H NMR spectroscopy.The results show a high selectivity for F-and AcO-,however,no obvious interaction was found for Cl-,Br-,and I-.The 1H NMR combined with Job curves indicates that a 1∶1 stoichiometry complex is formed between the receptors and the anions through hydrogen bonding interactions.In view of these results,the influences of the number of NH binding points and steric effect on binding properties were discussed.The receptor compound 3b can form much more hydrogen-bonding interactions due to the presence of many NH binding points,with larger association constant（Ks） than that of thiourea receptor.Compared compound 3a with 3b,large steric effect prevent the combination between compound 3a and anions.In terms of F-and AcO-,association constant of compound 3a and 3b followed the same tendency Ks（F-）Ks（AcO-）,owing to the better fit of size and shape between the receptors and F-.

关 键 词：分子钳 氨基硫脲 阴离子识别 

分 类 号：O611.5[理学—无机化学]