ONSO型Salen化合物的合成、单晶结构及金属离子识别

摘要

一些重金属离子即使在较低浓度时也会对环境、生物体产生毒性,所以研究痕量金属离子识别具有重大意义.荧光传感器由于具有选择性好、灵敏度高、成本低、实时响应等优点,得到了广泛关注.以2,4-二叔丁基苯酚,3,5-二叔丁基水杨醛和邻氨基苯硫酚为原料合成了类Salen配体L1,并用1 H NMR,13CNMR,IR,元素分析及X射线单晶衍射等手段对其进行了表征.并通过自由挥发法得到了配体L1的单晶结构,实验表明L1是三斜晶、P-1空间群的一个空穴平面[ONSO]四配位环境.通过荧光光谱考察了类Salen配体与金属离子(Li+,Na+,K+,Cd2+,Cs+,Co2+,Cu2+,Hg2+,Mn2+,Ni2+,Zn2+,Ag+)的识别与配位性能.光谱滴定分析表明L1与Zn2+以1∶1的化学计量数配位.另外,L1与Zn2+结合后荧光显著增强,荧光检测限达到5.01×10-5 mol·L-1,而上述提到的其他常见金属离子不引起荧光光谱变化.结果表明L1是一个对检测Zn2+的选择性高,灵敏度强的荧光增强型探针.%Some heavy metal ions can be toxic to the environment and organisms even with low concentrations,thus,it is of great significance to study trace metal ion recognition.Because of its good selectivity,high sensitivity,low cost and real-time response,the fluorescence sensor has been widely applied.A novel class salen ligand L1 was synthesized with 2,4-di-tert-butylphenol,3,5-di-tert-butyl-salicylaldehyde and 2-aminothiophenol.Its structure was characterized with 1H NMR,13 C NMR,IR,elemental analysis and X-ray single crystal techniques.The single crystal structure of ligand L1 was obtained with free evaporation method,and the experimental results show that L1 is a hole plane[ONSO] four coordination environment of three inclined and P-1 space group.The recognition properties of the target compound L1 with metal ions (Li+,Na+,K+,Cd2+,Cs+,Co2+,Cu2+,Hg2+,Mn2+,Ni2+,Zn2+,Ag+) had been investigated with fluorescence spectrophotometry.The binding of L1 to Zn2+ are in 1 ∶ 1 stoichometry.The results showed that L1 exhibited the selective recognition to Zn2+,and the detection limit was down to 5.01×10-5 mol · L-1.