基于[Dy4(μ4-O)]四面体结构单元的八核和十核镝簇合物的合成、结构及其单分子磁体行为研究

doi:10.6023/A12110865

化学学报 ›› 2013, Vol. 71 ›› Issue (02): 173-178.DOI: 10.6023/A12110865 上一篇下一篇

研究论文

基于[Dy₄(μ₄-O)]四面体结构单元的八核和十核镝簇合物的合成、结构及其单分子磁体行为研究

郭鹏虎, 廖小芬, 冷际东, 童明良

生物无机与合成化学教育部重点实验室光电材料与技术国家重点实验室中山大学化学与化学工程学院广州 510275

投稿日期:2012-11-05 发布日期:2012-12-06
通讯作者: 童明良 E-mail:tongml@mail.sysu.edu.cn
基金资助:
项目受973计划(No. 2012CB821704)和国家自然科学基金(Nos. 91122032, 90922009, 21121061)资助.

Synthesis, Structures and Single-Molecule Magnet Behaviour of Octanuclear and Decanuclear Dysprosium Clusters Based on [Dy₄(μ₄-O)] Tetrahedral Subunits

Guo Penghu, Liao Xiaofen, Leng Jidong, Tong Mingliang

Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education/State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China

Received:2012-11-05 Published:2012-12-06
Supported by:
Project supported by the “973 Project” (2012CB821704) and the National Natural Science Foundation of China (Nos. 91122032, 90922009 and 21121061).

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摘要/Abstract

通过溶剂热法合成了两个稀土簇合物, 其组成分别为: [Dy₈(bpt)₈(μ₄-O)₂(μ-OMe)₈(μ_1,1,3,3-N₃)(μ_1,3-N₃)(N₃)₂]· 11H₂O·9MeOH (1)和[Dy₁₀(bpt)₆(μ₄-O)₄(μ₃-OMe)₄(μ-OMe)₈(μ-OAc)₂(OAc)₂]·40H₂O (2) (Hbpt=3,5-双(2-吡啶基)-1,2,4-三氮唑). 1的簇核结构由两个[Dy₄(μ₄-O)]四面体通过罕见的μ_1,1,3,3和μ_1,3叠氮桥连接而成, 2则由四个共边连接的[Dy₄(μ₄-O)]四面体组成. 两个簇合物都表现出单分子磁体行为, 其中2是核数最高的纯稀土单分子磁体.

关键词: 单分子磁体, 镝, 弛豫, 簇合物, 叠氮

Two novel [Dy₄(μ₄-O)] based dysprosium(III) clusters, namely, [Dy₈(bpt)₈(μ₄-O)₂(μ-OMe)₈(μ_1,1,3,3-N₃)(μ_1,3-N₃)- (N₃)₂]·11H₂O·9MeOH (1) and [Dy₁₀(bpt)₆(μ₄-O)₄(μ₃-OMe)₄(μ-OMe)₈(μ-OAc)₂(OAc)₂]·40H₂O (2) (Hbpt=3,5-bis(pyridin- 2-yl)-1,2,4-trizole), are synthesized successfully. To obtain complex 1, a mixture of DyCl₃ (0.1 mmol), 2,2'-Hbpt (0.1 mmol) and NaN₃ (0.15 mmol) was sealed in a 25 mL vessel and then heated at 160℃ in methanol condition (8 mL) for 72 h. The reaction of Dy(OAc)₃ (0.17 mmol) and 2,2'-Hbpt (0.1 mmol) under the same condition as complex 1 yielded complex 2. Single-crystal X-ray diffraction reveals that complex 1 consists of a pair of [Dy₄(μ₄-O)] tetrahedral units bridged by two azido groups in μ_1,1,3,3 and μ_1,3 modes as well as two bpt ligands, while complex 2 possesses four edge-sharing [Dy₄(μ₄-O)] tetrahedral units. Magnetic susceptibility of polycrystalline samples were carried out using a SQUID magnetometer in the temperature range 2～300 K at 500 Oe dc field. The χ_MT value are 107.8 cm³·K·mol^-1 for complex 1 and 133.6 cm³·K·mol^-1 for complex 2 at 300 K, which are close to the expected values. The maximum values of magnetization at 1.8 K are 40.81 Nb and 51.62 Nb for 1 and 2, slightly smaller than the expected saturation values. For further investigation of the dynamic behaviour, ac susceptibility measurements were undertaken under zero-dc field between 1～1500 Hz, they both show temperature dependence and have maximum values in the χ_M″ vs v plots above 1.8 K, indicating the presence of slow relaxation of the magnetization. After linear fitting the first four points of ln(τ/s) vs 1/T plot, we get energy barrier U_eff=9.83(9) K, pre-exponential factor τ₀=1.63(2)×10^-5 s for 1, and U_eff=12.05(2) K, τ₀=6.75(8)×10^-7 s for 2 respectively. The bridging mode of azido in complex 1 is novel and complex 2 holds the record for highest nuclearity among the reported pure lanthanide single-molecule magnets (SMMs) under zero dc field.

Key words: single-molecule magnet, dysprosium, relaxation, cluster, azido

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郭鹏虎, 廖小芬, 冷际东, 童明良. 基于[Dy₄(μ₄-O)]四面体结构单元的八核和十核镝簇合物的合成、结构及其单分子磁体行为研究[J]. 化学学报, 2013, 71(02): 173-178.

Guo Penghu, Liao Xiaofen, Leng Jidong, Tong Mingliang. Synthesis, Structures and Single-Molecule Magnet Behaviour of Octanuclear and Decanuclear Dysprosium Clusters Based on [Dy₄(μ₄-O)] Tetrahedral Subunits[J]. Acta Chimica Sinica, 2013, 71(02): 173-178.

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基于[Dy₄(μ₄-O)]四面体结构单元的八核和十核镝簇合物的合成、结构及其单分子磁体行为研究

Synthesis, Structures and Single-Molecule Magnet Behaviour of Octanuclear and Decanuclear Dysprosium Clusters Based on [Dy₄(μ₄-O)] Tetrahedral Subunits

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