高等学校化学学报 ›› 2013, Vol. 34 ›› Issue (8): 1806-1811.doi: 10.7503/cjcu20130309

• 研究论文: 无机化学 • 上一篇    下一篇

以醚胺为模板剂合成含二价金属杂原子的开放骨架磷酸铝化合物M(Ⅱ)-CJ50

邵浪, 李乙, 王晓方, 于吉红   

  1. 吉林大学化学学院, 无机合成与制备化学国家重点实验室, 长春 130012
  • 收稿日期:2013-04-07 出版日期:2013-08-10 发布日期:2013-07-19
  • 通讯作者: 李乙,男,博士,副教授,主要从事微孔材料的合成与结构研究.E-mail:yili@jlu.edu.cn E-mail:yili@jlu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 21001049, 21273098)资助.

Synthesis of Divalent-metal-containing Open-framework Aluminophosphates M(Ⅱ)-CJ50 Using Ether Amine as the Organic Template

SHAO Lang, LI Yi, WANG Xiao-Fang, YU Ji-Hong   

  1. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China
  • Received:2013-04-07 Online:2013-08-10 Published:2013-07-19

摘要:

在水热体系中, 以2,2'-(乙烯二氧)双(乙胺)为模板剂, 合成了3种含二价金属杂原子的开放骨架磷酸铝化合物M(Ⅱ)-CJ50(|C6H17N2O2| [MAl3P4O16], 其中M=Mg, Mn和Fe). 单晶及粉末X射线衍射分析表明, 这3种化合物与以咪唑为模板剂合成的含三价金属杂原子的M(Ⅲ)-CJ50具有相似的骨架拓扑结构. 二者的区别在于: 由于使用了还原性较强的醚胺作模板剂, M(Ⅱ)-CJ50结构中的金属杂原子具有比M(Ⅲ)-CJ50更低的氧化态; M(Ⅱ)-CJ50中的金属杂原子与1个醚胺模板剂分子中的2个醚氧原子形成双齿配位, 而M(Ⅲ)-CJ50中的金属杂原子则与2个咪唑模板剂分别形成单齿配位. 此外, 磁性测试结果表明, 由于金属杂原子的氧化态以及配体模板剂分子的差异, 导致M(Ⅱ)-CJ50中的过渡金属杂原子处于电子高自旋态, 而M(Ⅲ)-CJ50中的杂原子则处于低自旋态.

关键词: 微孔材料, 磷酸铝, 金属杂原子, 有机模板剂, 水热合成

Abstract:

Three divalent-metal-containing open-framework aluminophosphates, designated M(Ⅱ)-CJ50, (|C6H17N2O2| [MAl3P4O16], M=Mg, Mn and Fe), have been hydrothermally synthesized using 2,2'-(ethylenedioxy)bis(ethylamine) as the organic template. Single crystal and powder X-ray diffraction analyses show that their structures are similar to those of trivalent-metal-containing aluminophosphates M(Ⅲ)-CJ50 synthesized by using imidazole as template. The differences between M(Ⅱ)-CJ50 and M(Ⅲ)-CJ50 are: hetero-metal atoms in M(Ⅱ)-CJ50 have lower oxidation states owing to the usage of ether amine; in M(Ⅱ)-CJ50, hetero-metal atoms are coordinated to the two O atoms in each ether amine molecule, whereas in M(Ⅲ)-CJ50 hetero-metal atoms are coordinated to pairs of imidazole molecules through single N atoms. Moreover, magnetic measurements reveal that the hetero-metal atoms in M(Ⅱ)-CJ50 are high-spin whereas those in M(Ⅲ)-CJ50 are low-spin owing to the differences in ligand molecules and oxidation states of hetero-metal atoms.

Key words: Microporous material, Aluminophosphate, Hetero-metal-atom, Organic template, Hydrothermal synthesis

中图分类号: