2,7-萘二磺酸导向构筑的五元瓜环-碱金属及碱土金属基超分子自组装体及其溶剂识别  

Construction and solvent recognition of cucurbit[5]uril‑alkali metal and alkali‑earth metal supramolecular self‑assembly induced by 2,7‑naphthalene disulfonic acid

作　　者：李婕 施静 肖帅 张明慧 葛伟伟 黄琳 陈凯 LI Jie;SHI Jing;XIAO Shuai;ZHANG Ming‑Hui;GE Wei‑Wei;HUANG Lin;CHEN Kai(Collaborative Innovation Center of Atmospheric Environment and Equipment Technology,Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control,Nanjing University of Information Science&Technology,Nanjing 210044,China)

机构地区：[1]南京信息工程大学环境科学与工程学院,江苏省大气环境与装备技术协同创新中心,江苏省大气环境监测与污染控制高技术研究重点实验室,南京210044

出　　处：《无机化学学报》2023年第9期1711-1720,共10页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21601090);江苏省高等学校基础科学(自然科学)研究重大项目(No.22KJA150002)资助。

摘　　要：以2,7-萘二磺酸(2,7-H_(2)NDA)作为结构导向剂,与五元瓜环(Q[5])和碱金属、碱土离子(K^(+)、Rb^(+)、Mg^(^(2+))、Ca^(^(2+)))在水热条件下制备出了4种新颖的Q[5]基超分子自组装体[K_(2)(H_(2)O)_(4)(Q[5])](2,7-NDA)·4H_(2)O(1)、[Rb_(2)(H_(2)O)_(5)(Q[5])](2,7-NDA)·3H_(2)O(2)、[Mg(H_(2)O)_(4)(Q[5])](2,7-NDA)·8H_(2)O(3)和[Ca(H_(2)O)_(4)(Q[5])](2,7-NDA)·10H_(2)O(4)。单晶X射线衍射测试结果表明,自组装体1和2具有相同的结构:Q[5]分子与金属离子配位形成的是“分子胶囊”;而在3中Q[5]与Mg^(2+)配位形成的是1∶1型简单配合物结构;在自组装体4中,Q[5]与Ca^(2+)配位形成的是一维Q[5]-Ca^(2+)配位聚合物链结构。这些结构中2,7-NDA^(2-)阴离子平衡了体系电荷,且通过其与瓜环外壁之间的弱相互作用,促进自组装体最终构筑成三维超分子结构。此外,还研究了自组装体4的溶剂识别荧光传感性能,结果表明其能够作为有机溶剂丙酮和DMF的猝灭型荧光探针。By introducing 2,7‑naphthalene disulfonic acid(H_(2)NDA)as a structure‑directed agent,four new Q[5]‑based supramolecular self‑assemblies,namely[[K_(2)(H_(2)O)_(4)(Q[5])](2,7-NDA)·4H_(2)O(1)、[Rb_(2)(H_(2)O)_(5)(Q[5])](2,7-NDA)·3H_(2)O(2)、[Mg(H_(2)O)_(4)(Q[5])](2,7-NDA)·8H_(2)O(3)and[Ca(H_(2)O)_(4)(Q[5])](2,7-NDA)·10H_(2)O(4),were prepared under hydrothermal conditions.Single crystal X‑ray diffraction results show that the self‑assemblies 1 and 2 have the same structure.The coordination of the Q[5]molecule with metal ions forms a“molecular capsule”structure in 1 and 2,while the coordination of Q[5]and Mg^(2+)in 3 forms a 1∶1 simple complex structure.In 4,Q[5]and Ca^(2+)can directly coordinate to form a 1D Q[5]‑Ca^(2+)coordination polymer chain structure.The 2,7‑NDA^(2-)anions in these structures balance the system charge,and through their outer‑surface interactions with Q[5],promote its final construction into a 3D supramolecular structure.In addition,we also studied the fluorescence sensing properties of self‑assembly 4,which could be used as quenching fluorescence probes for the organic solvents acetone and DMF.CCDC:2246647,1;2246648,2;2246649,3;2246650,4.

关 键 词：五元瓜环 外壁作用 超分子自组装体 荧光探针 溶剂识别 

分 类 号：O614.113[理学—无机化学] O614.114[理学—化学] O614.22O614.231