羧酸桥联的四核镧系簇合物的磁热效应和慢磁弛豫

引用本文: 刘遂军, 崔雨, 宋伟朝, 王庆伦, 卜显和. 羧酸桥联的四核镧系簇合物的磁热效应和慢磁弛豫[J]. 无机化学学报, 2015, 31(9): 1894-1902. doi: 10.11862/CJIC.2015.240 shu

Citation: LIU Sui-Jun, CUI Yu, SONG Wei-Chao, WANG Qing-Lun, BU Xian-He. Carboxylate-Bridged Tetranuclear Lanthanide Clusters: Magnetocaloric Effect and Slow Magnetic Relaxation[J]. Chinese Journal of Inorganic Chemistry, 2015, 31(9): 1894-1902. doi: 10.11862/CJIC.2015.240 shu

羧酸桥联的四核镧系簇合物的磁热效应和慢磁弛豫

刘遂军 ^1,2, ,
崔雨 ^1, ,
宋伟朝 ^1, ,
王庆伦 ^1, ,
卜显和 ^{1,
,}

1.
1. 南开大学化学系, 金属与分子基材料化学天津市重点实验室, 天津化学化工协同创新中心, 天津 300071;
2.
2. 江西理工大学冶金与化学工程学院, 赣州 341000

通讯作者: 卜显和,E-mail:buxh@nankai.edu.cn

基金项目:
国家自然科学基金(No.21290171) (No.21290171)

江西省科技厅青年自然科学基金(No.20151BAB213003)资助项目。 (No.20151BAB213003)

摘要: 在水热条件下,通过使用羧酸和螯合配体得到了一个系列的四核镧系簇合物,即[Ln₄(mnba)₁₂(tzp)₂(H₂O)₂](Ln=Gd(1),Tb(2),Er(3);Hmnba=间硝基苯甲酸;tzp=2-(1H-1,2,4-三唑-3-基)吡啶))。这3个化合物是同构的,且具有线性的四核簇结构。磁性研究表明,化合物1和3中簇内镧系离子之间是弱铁磁耦合的,但化合物2中铽离子之间是弱的反铁磁相互作用和(或)铽离子激发的斯塔克能级的去布居。化合物1具有较大的磁热效应(-ΔS_m^max=20.6 J·kg^-1·k^-1)。交流磁化率测试表明化合物3展现出频率和温度依赖的虚部信号,这是慢磁弛豫的典型特征,原因是铒离子的强各向异性和铁磁耦合的存在。

关键词:

羧酸;镧系簇合物;磁热效应;慢磁弛豫

English

Carboxylate-Bridged Tetranuclear Lanthanide Clusters: Magnetocaloric Effect and Slow Magnetic Relaxation

1.
1. Department of Chemistry, TKL of Metal- and Molecule-Based Material Chemistry and Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Nankai University, Tianjin 300071, China;
2.
2. School of Metallurgical and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou, Jiangxi 341000, China

Corresponding author: 卜显和,E-mail:buxh@nankai.edu.cn

Received Date: 08 June 2015
Fund Project:
国家自然科学基金(No.21290171)

江西省科技厅青年自然科学基金(No.20151BAB213003)资助项目。

Abstract: By using carboxylate and chelating ligands, a family of tetranuclear lanthanide clusters, namely [Ln₄(mnba)₁₂(tzp)₂(H₂O)₂] (Ln=Gd (1), Tb (2) and Er (3), Hmnba=m-nitrobenzoic acid, tzp=2-(1H-1, 2, 4-triazol-3-yl)pyridine), has been obtained under hydrothermal conditions. The three complexes exhibit linear tetranuclear clusters bridged by carboxylates with syn, syn-μ₂-η¹:η¹ mode. Magnetic investigation indicates weak ferromagnetic interaction between adjacent Gd^Ⅲ or Er^Ⅲ ions of the Ln₄ cluster in 1 and 3, while weak intra-molecular antiferromagnetic interaction between Tb^Ⅲ ions and/or depopulation of the Tb^Ⅲ excited Stark sub-levels in 2. Complex 1 exhibits a significant magnetocaloric effect with -ΔS_m^max=20.6 J·kg^-1·k^-1 and ac susceptibility measurements reveal frequency- and temperature-dependent out-of-phase signal under 5 kOe dc field in 3, being typical slow magnetic relaxation behavior due to strong anisotropy of Er^Ⅲ and ferromagnetic coupling.

Key words:

carboxylate;lanthanide clusters;magnetocaloric effect;slow magnetic relaxation

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

羧酸桥联的四核镧系簇合物的磁热效应和慢磁弛豫

通讯作者: 卜显和,E-mail:buxh@nankai.edu.cn

English

Carboxylate-Bridged Tetranuclear Lanthanide Clusters: Magnetocaloric Effect and Slow Magnetic Relaxation

Corresponding author: 卜显和,E-mail:buxh@nankai.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

羧酸桥联的四核镧系簇合物的磁热效应和慢磁弛豫

通讯作者: 卜显和,E-mail:buxh@nankai.edu.cn

English

Carboxylate-Bridged Tetranuclear Lanthanide Clusters: Magnetocaloric Effect and Slow Magnetic Relaxation

Corresponding author: 卜显和,E-mail:buxh@nankai.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

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