一种多孔配位聚合物的氢键协同客体响应

由硝酸锌、 吡唑-3,5-二羧酸（H₃pzdc）和2-氨基对苯二甲酸（H₂abdc）在溶剂热条件下反应得到一种多孔配位聚合物(Me₂NH₂)Zn₂(pzdc)(abdc)]·H₂O·DMF(1·g), 其中Me₂NH₂⁺由溶剂N,N-二甲基甲酰胺（DMF）水解得到, 1可视为平行排列的平整带状{Zn₂(pzdc)}⁺链被abdc^2-柱子交错支撑而成的三维多孔框架. 通过脱附/吸附溶剂分子, 中心对称的配位聚合物1·g可以可逆转变成手性的(Me₂NH₂)Zn₂(pzdc)(abdc)](1′). 单晶结构分析表明, 在客体响应过程中, 基于框架、 抗衡离子和客体分子之间的氢键协作与竞争, 抗衡离子发生了显著的移动 和转动, 导致{Zn₂(pzdc)}⁺链扭曲和转动, 伴随着超过10%的晶胞体积和孔洞率变化. 气体吸附测试表明, 化合物1'对N₂和CO₂存在不同的结构响应行为.

Guest-responses of A Porous Coordination Polymer Based on Synergistic Hydrogen Bonds

Solvothermal reaction of Zn（NO₃）₂·6H₂O， pyrazole-3， 5-dicarboxylic acid （H₃pzdc） and 2-amino-1，4-benzenedicarboxylic acid （H₂abdc） in N，N-dimethylformamide（DMF） produced a porous coordination polymer（Me₂NH₂）［Zn₂（pzdc）（abdc）］·H₂O·DMF（1·g， g means guest molecules， H₂O and DMF）， in which Me₂NH₂⁺ was generated from the hydrolysis of the solvent DMF. The 3-dimensional porous coordination framework of 1 can be regarded as a pillared-ribbon structure consisting of parallelly-aligned flat ｛Zn₂（pzdc）｝⁺ ribbons and abdc^2- pillars. via desorption/adsorption of solvent molecules， centrosymmetric 1·g can reversibly transform to a chiral framework （Me₂NH₂）［Zn₂（pzdc）（abdc）］（1'）. Single-crystal X-ray diffraction analyses showed that， based on the competition and cooperation of hydrogen bonds among the host framework， counter cations， and neutral guest molecules， the counter cations underwent significant movement and rotation in the guest-responsive structural transformations， giving rise to the distortion and rotation of the ｛Zn₂（pzdc）｝⁺ ribbon， as well as more than 10% changes of the unit-cell volume and void ratio. Gas adsorption measurements of 1' showed different responses toward N₂ and CO₂.