含噁二唑大环冠醚的合成、结构及金属离子识别性能  

Synthesis,Structure and Recognition Properties of Macrocyclic Crown Ethers with Oxadiazole

作　　者：田霞[1] 杨福群 袁伟 赵雷 姚雷 甄小丽[1] 韩建荣[1] 刘守信 TIAN Xia;YANG Fuqun;YUAN Wei;ZHAO Lei;YAO Lei;ZHEN Xiaoli;HAN Jianrong;LIU Shouxin(College of Science,Hebei University of Science&Technology;State Key Laboratory Breeding Base-Hebei Province Key Laboratory of Molecular Chemistry for Drug,Hebei University of Science&Technology,Shijiazhuang 050018,China)

机构地区：[1]河北科技大学理学院 [2]河北省药用分子化学重点实验室,石家庄050018

出　　处：《高等学校化学学报》2020年第3期490-497,共8页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21272052)资助~~

摘　　要：合成了含有1,3,4-噁二唑基团的大环冠醚:2,3,11,12-二苯并-4,7,10,16-四氧-14,15-二氮杂双环[11.2.1]-十六烷-13,15-二烯(2)、2,3,14,15-二苯并-4,7,10,13,19-五氧-17,18-二氮杂双环[14.2.1]-十九烷-16,18-二烯(3)和2,3,17,18-二苯并-4,7,10,13,16,22-六氧-20,21-二氮杂双环[17.2.1]-二十二烷-19,21-二烯(4),并培养得到其单晶;通过核磁共振波谱、高分辨质谱及X射线单晶衍射对其结构进行了表征.结果表明,冠醚2属正交晶系,Pna 21空间群;冠醚3属于单斜晶系,C 2/c空间群;冠醚4属正交晶系,Pbca空间群.在3个主体化合物中均存在分子间氢键和π-π相互作用将分子连接成三维空间结构.采用荧光光谱测定了开链冠醚2,5-二[2-(2-甲氧乙氧基)苯基]-1,3,4-噁二唑(1)和不同环空腔大小的噁二唑冠醚(2~4)对金属离子Li+,Na+,K+,Rb+,Mg 2+和Ca 2+的键合行为.研究结果表明,开链冠醚1和冠醚4对碱土金属Mg 2+和Ca 2+表现出荧光猝灭行为,且对Ca 2+表现出良好的键合能力和选择性;而冠醚2对Na+和K+表现出良好的键合能力,但其Na+/K+的选择性较差.A series of macrocyclic crown ethers containing oxadiazole groups were synthesized and their single crystals were obtained.Their structures were characterized by nuclear magnetic resonance(NMR),high resolution electrospray ionization mass spectroscopy(HRESI-MS)and X-ray single crystal diffraction.The single crystal X-ray diffraction revealed that 2,3,11,12-dibenzo-4,7,10,16-tetraoxa-14,15-diazabicyclo[11.2.1]-hexadecane-13,15-diene(2)belonged to orthorhombic crystal system with space group Pna 21,2,3,14,15-dibenzo-4,7,10,13,19-pentaoxa-17,18-diazabicyclo[14.2.1]-nonadecane-16,18-diene(3)belongs to monoclinic crystal system with space group C 2/c and 2,3,17,18-dibenzo-4,7,10,13,16,22-hexaoxa-20,21-diazabicyclo[17.2.1]-docosadecane-19,21-diene(4)belonged to orthorhombic crystal system with space group Pbca.Three crown ethers were all connected to form a three-dimensional supramolecular structure by CH…O or CH…N hydrogen bond intramolecular andπ-πstacking.The bonding behaviors of 2,5-bis[2-(2-methoxyethoxy)phenyl]-1,3,4-oxadiazole(1)and crown ethers 24 with different sizes to metal ions Li^+,Na^+,K^+,Rb^+,Mg^2+and Ca^2+was determined by fluorescence spectroscopy.The results showed that open-chain crown ether 1 and macrocyclic crown ether 4 exhibited fluorescence quenching behavior and good bon-ding ability and selectivity on alkaline earth metal Ca^2+.While crown ether 2 showed good bonding ability to Na^+and K^+and poor Na^+/K^+selectivity.

关 键 词：1 3 4-噁二唑 冠醚 阳离子识别 晶体结构 荧光光谱 

分 类 号：O626[理学—有机化学]