【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,Pna21空间群;冠醚3属于单斜晶系,C2/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⁺,Mg²⁺和Ca²⁺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Mg²⁺和Ca²⁺表现出荧光猝灭行为,且对Ca²⁺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.更多还原

【Abstract】 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 Pna21,2,3,14,15-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 C2/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 C—H…O or C—H…N hydrogen bond intramolecular and π-π stacking. The bonding behaviors of 2,5-bis[2-（ 2-methoxyethoxy） phenyl]-1,3,4-oxadiazole（ 1） and crown ethers 2—4 with different sizes to metal ions Li⁺,Na⁺,K⁺,Rb⁺,Mg²⁺and Ca²⁺was determined by fluorescence spectroscopy. The results showed that openchain crown ether 1 and macrocyclic crown ether 4 exhibited fluorescence quenching behavior and good bonding ability and selectivity on alkaline earth metal Ca²⁺. While crown ether 2 showed good bonding ability to Na⁺and K⁺ and poor Na⁺/K⁺ selectivity.更多还原