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作 者:辛凌云[1] 李云平[1] 鞠丰阳[2] 李晓玲[1] 刘广臻[1]
机构地区:[1]洛阳师范学院化学化工学院,河南省功能导向多孔材料重点实验室,洛阳471934 [2]洛阳师范学院食品与药品学院,洛阳471934
出 处:《无机化学学报》2017年第8期1474-1480,共7页Chinese Journal of Inorganic Chemistry
基 金:国家自然科学基金(No.21571093);河南省高校科技创新人才(No.14HASTIT017);河南省高校科技创新团队(No.14IRTSTHN008);河南省科技攻关计划(No.162102210304);河南省社会发展(No.152102310348)资助项目
摘 要:通过溶剂热方法合成了一个由氢键拓展的携带路易斯碱位的三维超分子配位聚合物:{[Cd(HTZ-IP)(HPYTZ)(H_2O)_2]·5H_2O}n(HTZ-H_2IP=5-(5-四氮唑基)间苯二甲酸;HPYTZ=3,5-(4-吡啶基)-1,2,4-三唑]。X射线单晶衍射结果表明,中心镉离子由含氮杂环羧酸配体和富氮辅助配体连接成"有悬挂手臂"的一维链,而链间则凭借配位水和2个配体的氢键作用拓展成三维超分子化合物。有趣的是配合物存在大量裸露的未配位的N原子,此N原子具有路易斯碱性质,能与路易斯酸性质的Ag^+有效结合,从而引起配合物的荧光猝灭。该性质能在无色溶液中有效检测10^(-4)~10^(-6) mol·L^(-1)范围内的痕量Ag^+离子。Hydrogen-bonded network with Lewis basic N sites have been obtained by the solvothermal reaction, named {[Cd(HTZ-IP)(HPYTZ)(H2O)2]5H2O}n (HTZ-H2IP=5-(tetrazol-5-yl)isophthalic acid, HPYTZ=3,5-di(4-pyridyl)-1,2,4-triazolate ligand). The single-crystal X-ray diffraction analysis shows the adjacent Cd(Ⅱ) centers are bridged by HTZ-H2IP ligand to form Cd carboxylate linear chains, while each HPYTZ molecule works as a terminal ligand with uncoordinated pyridine N atoms. The paralleled chains are connected by H-bonds between coordination H2O and two ligands to produce its 3D supramolecular network. It is interesting that the network possess uncoordinated N atoms (Lewis-base sites) existing a significant quenching effect to the luminescent intensity of complex by Ag ion. As a sensing material for Ag, this coordinated polymer has features including simple preparation procedure, fast detection time, excellent selectivity for Ag in colorless solution, and high sensitivity with a detection range of 10-4~10-6 molL-1 concentration limit.
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