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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (12): 1199-1204. 上一篇    下一篇

研究论文

配位聚合物M(H2O)2[Ni(CN)4]•xH2O的合成、晶体结构及性能研究

陆润芹，陈莺莺，周虎，袁爱华*   

  1. 江苏科技大学材料科学与工程学院 镇江 212003
  • 投稿日期:2009-09-15 修回日期:2009-11-17 发布日期:2010-02-25
  • 通讯作者: 袁爱华
  • 基金资助:

    江苏省高校自然科学基金(No. 07KJB150030)

2O)2[Ni(CN)4]•xH2O

LU Run-Qin, CHEN Ying-Ying, ZHOU Hu, YUAN Ai-Hua   

  • Received:2009-09-15 Revised:2009-11-17 Published:2010-02-25

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以[Ni(CN)4]2－为构筑基元, 与过渡金属离子Mn2＋通过溶液缓慢扩散法合成出二维Hofmann类氰基桥联配位聚合物Mn(H2O)2[Ni(CN)4]•4H2O (1), 并解析了其晶体结构. 配位聚合物1属正交晶系, 空间群Cmcm, 晶胞参数a＝0.73080(5) nm, b＝1.21372(8) nm, c＝1.40875(9) nm, α＝β＝γ＝90°, Ni和Mn中心通过氰桥交互连接构成二维波浪形层状结构. 通过混合法得到系列Hofmann类配位聚合物M(H2O)2[Ni(CN)4]•xH2O (M＝Mn, Fe, Co, Ni, Cd)的粉末样品, 粉末XRD结果表明, 系列配位聚合物具有与1相同的晶体结构; 变温粉末XRD和热重分析结果表明, 系列配位聚合物具有较高的热稳定性. 以Mn(H2O)2[Ni(CN)4]•xH2O的脱水样品为构筑模块与柱状配体pyrazine组装构筑的三维多孔配位聚合物具有一定的储气性能.

关键词: Hofmann类, 配位聚合物, [Ni(CN)4]2－, 晶体结构, 吸附

A 2D Hofmann-type cyano-bridged coordination polymer Mn(H2O)2[Ni(CN)4]•4H2O (1) has been synthesized by self-assembly based on [Ni(CN)4]2－ and Mn2＋ as building blocks. The single crystals were obtained successfully by slow solution diffusion method and the crystal structure has been solved. 1 belongs to orthorhombic system, space group Cmcm, cell parameters: a＝0.73080(5) nm, b＝1.21372(8) nm, c＝1.40875(9) nm, α＝β＝γ＝90°. Ni and Mn centers are connected by cyano-bridges alternately, resulting in 2D undulate sheets. A series of powder samples M(H2O)2[Ni(CN)4]•xH2O (M＝Mn, Fe, Co, Ni, Cd) have been synthesized by quick mixing method, which are isostructural with 1 confirmed by PXRD patterns. VT-PXRD and TG analysis indicate that these coordination polymers are of high stability. A 3D porous coordination polymer has been constructed with dehydrated sample of Mn(H2O)2[Ni(CN)4]•xH2O and pillared ligand pyrazine, which exhibits gas storage property.

Key words: Hofmann-type, coordination polymer, [Ni(CN)4]2－, crystal structure, adsorption