层状钴有机膦酸化合物的合成以及变磁行为

doi:10.6023/A12100839

化学学报 ›› 2013, Vol. 71 ›› Issue (04): 555-559.DOI: 10.6023/A12100839 上一篇下一篇

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

南京大学配位化学国家重点实验室 210093

投稿日期:2012-10-30 发布日期:2013-01-25
通讯作者: 郑丽敏 E-mail:lmzheng@nju.edu.cn
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.

Layered Cobalt Phosphonate with Metamagnetism

Cai Zhongsheng, Bao Songsong, Zheng Limin

State Key Laboratory of Coordination Chemistry, Nanjing University 210093

Received:2012-10-30 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/Abstract

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

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 H_SF of 28.0 kOe at 1.8 K. CCDC: 908112 (1), 908113 (2).

Key words: layer, cobalt, phosphonate, metamagnetism

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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.

Cai Zhongsheng, Bao Songsong, Zheng Limin. Layered Cobalt Phosphonate with Metamagnetism[J]. Acta Chimica Sinica, 2013, 71(04): 555-559.

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层状钴有机膦酸化合物的合成以及变磁行为

Layered Cobalt Phosphonate with Metamagnetism

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