两个4-连接配位网络的锌(Ⅱ)配位聚合物的合成、结构和荧光性质

Synthesis, Structure and Fluorescent Properties of Two Zn(Ⅱ) Coordination Polymers with 4-Connected Coordination Network

以5-氨基四氮唑(HATz),异烟酸(HPyc)和ZnSO4·7H2O或Zn(NO3)2·6H2O为反应物,在DMF溶剂热条件下分别得到了2个锌(Ⅱ)配位聚合物{[(CH3)2NH2]·[Zn(ATz)(SO4)]}n(1)和{[Zn(ATz)(Pyc)]·0.5DMF}n(2),并对它们的组成和结构进行了表征。配合物1是由4-连接(4,4)网络拓扑的[Zn(ATz)(SO4)]nn-二维阴离子层和[(CH3)2NH2]+阳离子间通过氢键作用形成的二维波浪层结构。配合物2则是1个二重穿插的4-连接金刚烷拓扑的三维微孔金属-有机框架结构,客体DMF分子填充在孔道内。室温下的固体荧光实验表明,在350 nm的光激发下,配合物1和2分别在为445 nm和458 nm处出现强烈的荧光发射。

Reactions of 5-amino-tetrazole （HATz） and 4-pyridinecarboxylic acid （HPyc） with ZnSO4·7H2O or Zn（NO3）2·6H2O under N,N＇-dimethylformamide （DMF） solvothermal condition, yielded two new Zn（Ⅱ） coordination polymers of {[（CHa）2NHz]＇[Zn（ATz）（SO4）]}n （1） and {[Zn（ATz）（Pyc）] ·0.5DMF}n （2）, respectively, which have been structurally characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. The results of structural analysis reveal that complex 1 possesses an 2D undulated layer structure, in which 2D anion （4,4） layer of [Zn（ATz）（SO4）]n^n- and [（CH3）2NH2]＋ cations are assembled together via strong hydrogen bonding interactions. A remarkable feature of complex 2 is a two-fold interpenetrating 3D microporous metal-organic framework with 4-connected diamondoid topology, in which free DMF molecules locate in the channels. Luminescent properties studies indicate that complexes 1 and 2 exhibit intense fluorescent emissions at λmax=445 nm and 458 nm when excited at 350 nm, respectively, in the solid state at room temperature. CCDC： 921342, 1; 921343, 2.