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2013 , Vol. 71 >Issue 04: 555 - 559

DOI: https://doi.org/10.6023/A12100839

研究论文

层状钴有机膦酸化合物的合成以及变磁行为

  • 蔡中胜 ,
  • 鲍松松 ,
  • 郑丽敏
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  • 南京大学 配位化学国家重点实验室 210093

收稿日期: 2012-10-30

  网络出版日期: 2013-01-25

基金资助

项目受科技部重大研究计划(No. 2010CB923402)和江苏省自然科学基金(No. BK2009009)资助.

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Layered Cobalt Phosphonate with Metamagnetism

  • Cai Zhongsheng ,
  • Bao Songsong ,
  • Zheng Limin
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  • State Key Laboratory of Coordination Chemistry, Nanjing University 210093

Received date: 2012-10-30

  Online published: 2013-01-25

Supported by

Project supported by the National Basic Research Program of China (No. 2010CB923402) and the Natural Science Foundation of Jiangsu Province of China (No. BK2009009).

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摘要

从配体C6H5CH2N(CH2PO3H2)2 (H4L)出发, 在水热条件下得到了两个层状结构化合物Co2(L)(H2O)2·0.3H2O (1)和Co2(L)(H2O) (2). 在这两个化合物的层结构中分别存在“之”字型和“蝴蝶”型的{Co4O6}四核簇结构单元, 相邻四核通过O-P-O桥连形成二维无机层状结构, 有机基团位于层与层之间. 磁性测试表明, 化合物1中存在反铁磁耦合, 并且在低温下表现出场致变磁行为; 我们还对化合物1的脱水样品(1-de)进行了磁性测试, 测试结果表明化合物1-de存在自旋翻转现象. CCDC: 908112 (1), 908113 (2).

关键词： 层状; 钴; 有机膦酸; 变磁

本文引用格式

蔡中胜 , 鲍松松 , 郑丽敏 . 层状钴有机膦酸化合物的合成以及变磁行为[J]. 化学学报, 2013 , 71(04) : 555 -559 . DOI: 10.6023/A12100839

Abstract

Two layered cobalt phosphonates, namely, Co2(L)(H2O)2·0.3H2O (1) and Co2(L)(H2O) (2) (H4L＝C6H5CH2N- (CH2PO3H2)2) have been synthesized under hydrothermal condition. Single-crystal X-ray diffraction determinations reveal that compound 1 crystallizes in triclinic space group P-1, with a＝6.320(1) Å, b＝9.484(1) Å, c＝12.705(1) Å, α ＝ 91.7(1)°, β＝ 96.2(1)°, γ ＝103.9(1)°, V＝733.8(1) Å3, Z＝2 and compound 2 crystallizes in monoclinic space group P21/c, with a＝14.165(2) Å, b＝9.574(1) Å, c＝10.072(1) Å, β＝102.5(1)°, V＝1333.4(3) Å3, Z＝4. Both compounds display layered structures in which the inorganic layers made up of tetranuclear clusters of {Co4O6} and {PO3C} linkages are separated by the methylphenyl groups. However, the tetranuclear clusters are different in the two compounds. In 1, the {Co4O6} cluster is composed of edge-sharing {Co(1)NO5} and {Co(2)O6} octahedra in a zigzag arrangement. While in 2, the equivalent edge-sharing {Co(1)NO5} octahedra are each corner-shared with the {Co(1)O5} triangular bipyramids, forming a butterfly-like tetramer. Magnetic measurements are conducted for compound 1 which shows a dominant antiferromagnetic interactions between the Co(II) centers. Moreover, metamagnetism is observed for 1 at low temperature with a critical field of 26.0 kOe at 2 K. The dehydrated sample, 1-de, was also prepared by heating 1 at 180 ℃ for 20 min. Magnetic measurement reveals that 1-de exhibits field-induced spin-flop transition with HSF of 28.0 kOe at 1.8 K. CCDC: 908112 (1), 908113 (2).

Key words： layer; cobalt; phosphonate; metamagnetism

参考文献

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[12] Structural data for compound 1: triclinic, space group P-1, a＝6.320(1) Å, b＝9.484(1) Å, c＝12.705(1) Å, α＝91.7(1)°, β ＝96.2(1)°, γ ＝103.9(1)°, V＝733.8(1) Å3, Z＝2.

[13] Structural data for compound 2: monoclinic, space group P21/c, with a＝14.165(2) Å, b＝9.574(1) Å, c＝10.072(1) Å, β＝102.5(1)°, V＝1333.4(1) Å3, Z＝4.

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