氨基脲衍生物的合成及其阴离子识别性能

Synthesis and anion recognition properties of a semicarbazide derivative

以3-异氰酸丙基三乙氧基硅烷和2,4-二硝基苯肼为原料,制备了一种氨基脲衍生物阴离子受体R,通过1HNMR、^(13)CNMR、FTIR和HRMS对其结构进行了表征。在二甲基亚砜(DMSO)体系,受体R通过UV-Vis吸收光谱的变化及溶液颜色的显著差别对F^(–)、CH_(3)COO–(Ac^(–))和CN^(–)表现出良好的识别能力。此外,通过向DMSO体系中加入体积分数30%竞争溶剂H2O可以实现对CN^(–)的单一识别。根据Benesi-Hidebrand方程,受体R识别CN^(–)的络合常数为8.58×10^(3)L/mol,且检出限为1.470μmol/L。Job曲线分析证实,受体R与F^(–)通过氢键以物质的量比为1∶1形成配合物。^(1)HNMR滴定及理论计算表明,受体R与阴离子是以氢键形式相结合的识别机制,未发现脱质子过程。

A semicarbazide derivative anion receptor R was synthesized using 3-propyl isocyanate triethoxysilane and 2,4-dinitrophenylhydrazine as raw materials and characterized by^(1)HNMR,^(13)CNMR,FTIR and HRMS.Receptor R exhibited excellent recognition capability for F^(–),CH_(3)COO–(Ac^(–))and CN^(–)by obvious changes of UV-Vis spectra and solution color in dimethyl sulfoxide(DMSO)system.In addition,the single recognition of receptor R on CN^(–)could be achieved by adding volume fraction 30%of competing solvent H_(2)O into DMSO system.According to the Benesi-Hidebrand equation,receptor R recognized CN^(–)with a complexing constant of 8.58×10^(3)L/mol and a detection limit of 1.470μmol/L.The Job curve analysis confirmed that the receptor R and F^(–)formed a complex by hydrogen bonding at a molar ratio of 1∶1.1HNMR titration and theoretical calculation indicated that the recognition mechanism of receptor R for anions by hydrogen bonding,and no deprotonation behavior was found.