行政院國家科學委員會補助專題研究計畫 ⌧成果報告
□期中進度報告 分子磁鐵的磁性化學
計畫類別：
7個別型計畫 □整合型計畫
計畫編號：NSC 96－2113－M －006 －010－MY3 執行期間：96 年 08 月 01 日 至 99 年 07 月 01 日 執行機構及系所：成功大學化學系
計畫主持人：蔡惠蓮 共同主持人：
計畫參與人員：楊振宜,蔡育哲,鄭凱鴻,楊智文,蘇煜中,洪紹博,李垠輯,黃于東, 劉名軒,何秉澔
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7完整報告
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中 華 民 國 99 年 10 月 31 日
目錄 頁次
一、中英文摘要及關鍵詞 1
1、中文摘要 1 2、英文摘要 1 二、報告內容 2
1、Inorganic Chemistry 2008, 47, 10184-10186. 3
2、Polyhedron, 2009, 28, 1842-1851. 6
3、Chemical Communications, 2010, 5716-5718 16
4、 Inorganic Chemistry 2010, 49, 7817-7619 19
三、參考文獻 22
一、 中英文摘要及關鍵詞
1、中文摘要
報 導 [Mn3O(Me-salox)3(2,4′-bpy)3(ClO4)]·0.5MeCN (1·0.5MeCN) (Me-H2salox = 2-hydroxyphenylethanone oxime) ， [Mn6O2(salox)6(MeOH)6(NCNCONH2)2] (2) (H2salox = salicylaldoxime) ， [Mn6O2(salox)6(EtOH)4(H2O)2Cl2] (3) ， 及 [Mn6O2(4-MeOsalox)6(N3)4(MeOH)4]n (4·) (4-MeO-H2salox = 2-hydroxy-4-methoxy-benzaldehyde oxime)，(NEt4)2n[Mn8O2(salox)6(N3)8(MeOH)3]n (5) 的合成、磁性及結構。為[Mn3III(μ3-O)]7+的結構化合物，以η1:η1:η1:μ-R-salox2-配位三角平面，化合物(1) 的 Mn-N-O-Mn 扭 曲 角 度 大 於 40 ， 以 致 金 屬 間 為 鐵 磁 作 用 ， 其 基 態 S = 6 為 單 分 子 磁 鐵 。 [Mn6O2(salox)6(MeOH)6(NCNCONH2)2] (2) 和 [Mn6O2(salox)6(EtOH)4(H2O)2Cl2] (3) 含 有 已 知 的 [MnIII6(μ3-O)2]14+核心結構，從 dc 磁化率測量得其基態S = 4 為單分子磁鐵，及 D = -0.82 cm-1 (化合物 2) D = -1.18 cm-1 (化合物 3)。化合物 2 和 3 從 ac 磁化率測量得化合物 2 的 Ueff = 27.0(1) K 及τ0 = 3.8(2)
× 10-9 s，化合物 3 的 Ueff of 25.1(6) K 及τ0 = 4.6(1) × 10-8 s。另外兩個單鏈磁鐵化合物 4 及化合物 5 都
有ac 磁化率測量及磁滯迴路。
關鍵詞：單分子磁鐵、單鏈磁鐵、磁滯迴路 2、Abstract
A trinuclear manganese complex, [Mn3O(Me-salox)3(2,4′-bpy)3(ClO4)]·0.5MeCN (1·0.5MeCN) (Me-H2salox = 2-hydroxyphenylethanone oxime), has been synthesized and characterized structurally as a [MnIII3(μ3-O)]7+ core. Structural distortion by the twisting of oxime ligand dominates ferromagnetic interactions within three Mn ions to give an S = 6 ground state, as well as enhance the anisotropy barrier Ueff
to 37.5 K. Both [Mn6O2(salox)6(MeOH)6(NCNCONH2)2] (2) (H2salox = salicylaldoxime) and [Mn6O2(salox)6(EtOH)4(H2O)2Cl2] (3) contain a [MnIII6(μ3-O)2]14+ core, which is a known structural type in the family of Mn6 complexes. Both complexes 2 and 3 have the ground state spin value of S = 4, with significant magnetoanisotropy as gauged by the D value of -0.82 cm-1 and -1.18 cm-1, for 2 and 3 respectively.
Both complexes 2 and 3 indicates the slow magnetic relaxation of superparamagnetic behaviour with a Ueff of 27.0(1) K and τ0 = 3.8(2) × 10-9 s for complex 2, and Ueff of 25.1(6) K andτ0 = 4.6(1) × 10-8 s for complex 3.
A manganese single-chain magnet, [Mn6O2(4-MeOsalox)6(N3)4(MeOH)4]n (4-MeO-H2salox = 2-hydroxy-4-methoxy-benzaldehyde oxime) (4), is synthesized via the assembly of Mn6 single-molecule magnets, which exhibits a large magnetic coercivity. Another one dimensional chain containing a mixed-valence octanuclear manganese(II,III) building unit, (NEt4)2n[Mn8O2(salox)6(N3)8(MeOH)3]n (5), was synthesized and characterized structurally and magnetically. Each building unit contains a [MnII2MnIII6O2]18+ structural topology. The frequency dependence of the out-of-phase component in alternating current magnetic susceptibilities and hysteresis loops for the complex indicates SCM-like behavior.
Keywords: single-molecule magnet, single-chain magnet, hysteresis loop
二、 報告內容
已發表的四篇論文為成果報告內容:
1. Chen-I Yang, Wolfgang Wernsdorfer, Kai-Hung Cheng, Motohiro Nakano, Gene-Hsiang Lee, Hui-Lien Tsai*
A [MnIII3O]7+ Single-Molecule Magnet: the Anisotropy Barrier Enhanced by Structural Distortion Inorganic Chemistry 2008, 47, 10184-10186.
2. Chen-I Yang, Shao-Po Hung, Motohiro Nakano, Gene-Hsiang Lee, and Hui-Lien Tsai*
Synthesis, structures and magnetic properties of two hexanuclear complexes Polyhedron, 2009, 28, 1842-1851.
3. Chen-I Yang, Yu-Jhe Tsai, Shao-Po Hung, Hui-Lien Tsai,* Motohiro Nakano* A Manganese Single-Chain Magnet Exhibits a Large Magnetic Coercivity Chemical Communications, 2010, 5716-5718.
4. Chen-I Yang, Shao-Po Hung,Gene-Hsiang Lee, Motohiro Nakano,Hui-Lien Tsai* Slow Magnetic Relaxation in An Octanuclear Manganese Chain ″
Inorganic Chemistry 2010, 49, 7817-7619.
三、參考文獻
1. 執行本計畫相關之著作:
1. 蔡育哲,鄭凱鴻,蔡惠蓮*
2008, March
″含錳金屬簇單分子磁鐵的結構簡介″
化學 2008, 66, 7-17.
2. Chen-I Yang, Wolfgang Wernsdorfer, Kai-Hung Cheng, Motohiro Nakano, Gene-Hsiang Lee, Hui-Lien Tsai*
″A [MnIII3O]7+ Single-Molecule Magnet: the Anisotropy Barrier Enhanced by Structural Distortion″
Inorganic Chemistry 2008, 47, 10184-10186.
3. Chen-I Yang, Shao-Po Hung, Motohiro Nakano, Gene-Hsiang Lee, and Hui-Lien Tsai *
″Synthesis, structures and magnetic properties of two hexanuclear complexes″
Polyhedron, 2009, 28, 1842-1851.
4. Huey-Ting Chung, Hui-Lien Tsai, En-Che Yang, Po-Hsiu Chien, Chia-Chien Peng, Yun-Chieh Huang, and Yen-Hsiang Liu*
"A New Manganese Coordination Polymer Containing 1,2,4-Benzenetricarboxylic Acid "
European Journal of Inorganic Chemistry 2009, 3661-3666.
5. Way-Zen Lee,* Huan-Sheng Tseng, Hui-Lien Tsai,* and Ting-Shen Kuo
″Bio-inspired Catalytic Conjugate Additions of Thiophenols to α,β-Enones by a Disubstituted Benzoate-Bridged Nickel Mimic for the Active Site of Urease″
Organometallics 2010, 29 (13), 2874-2881.
6. Chen-I Yang, Yu-Jhe Tsai, Shao-Po Hung, Hui-Lien Tsai,* Motohiro Nakano*
″ A Manganese Single-Chain Magnet Exhibits a Large Magnetic Coercivity ″ Chemical Communications, 2010, 5716-5718.
7. Chen-I Yang, Shao-Po Hung,Gene-Hsiang Lee, Motohiro Nakano,Hui-Lien Tsai*
″ Slow Magnetic Relaxation in An Octanuclear Manganese Chain ″ Inorganic Chemistry 2010, 49, 7817-7619
8. Tien-Wen Tseng,* Tzuoo-Tsair Luo, Cheng-Chuan Tsai, Jing-Yun Wu, Hui-Lien Tsai, Kuang-Lieh Lu
″Crystal Engineering of Three Net-to-Net Intersecting Metal–Organic Frameworks from Two Comparable Organic Linking Squares″
European Journal of Inorganic Chemistry, 2010, 24, 3750-3755.
2. 會議論文
1. 中國化學會九十六年年會暨第十一屆台北國際化學會議, 2007, Dec. 12-15.
Yu-Jhe Tsai (蔡育哲), Kai-Hung Cheng (鄭凱鴻),Gene-Hsiang Lee (李錦祥), Hui-Lien Tsai (蔡惠 蓮)*
Synthesis, Crystal Structure and Magnetic Properties of Penta- and Hexanuclear Manganese Complexes
2. 中國化學會九十六年年會暨第十一屆台北國際化學會議, 2007, Dec. 12-15.
Hui-Lien Tsai(蔡惠蓮), Chen-I Yang (楊振宜), Wolfgang Wernsdorfer, Yu-Jhe Tsai(蔡育 哲), Gene-Hsiang Lee(李錦祥)
The [Mn3O]7+ Trianglar Core As A Building Unit For New Molecular Magnets 3. Hui-Lien Tsai, Yu-Jhe Tsai, Gene-Hsiang Lee
″Magnetic Relaxations of a Pentanuclear Manganese Complex″
The 21st IUCr Satellite Meeting “Molecular Crystals Exhibiting Exotic Functions”, 2008, August 21-22, Osaka, Japan
4. Yu-Jhe Tsai, Kai-Hung Cheng, Gene-Hsiang Lee, Hui-Lien Tsai
″A pentanuclear manganese single-molecule magnet with a ground state S = 11″
JEMS 08 - Joint European Magnetic Symposia, 2008, September 14-19, Dublin, Ireland 5. Chen-I Yang, Kai-Hung Cheng, Motohiro Nakano, Gene-Hsiang Lee, Hui-Lien Tsai*
″ Synthesis, structures and magnetic properties of two hexanuclear complexes″
The 11th International Conference on Molecule-based Magnets, ICMM, 2008, September 21-24, Florence, Italy.
6. 中國化學九十七年年會, 2008, Nov. 24-26
Kai-Hung Cheng (鄭凱鴻), Chen-I Yang (楊振宜), Wolfgang Wernsdorfer, Gene-Hsiang Lee (李 錦祥), Hui-Lien Tsai(蔡惠蓮)*
″ [Mn3O]7+ complexes: Structural Distortion Influence Magnetic Properties″
7. American Physical Society March Meeting, 2009, March11 – 19, Pittsburgh, PA, USA.
Emalee Popoff, Salvador Barraza-Lopez, Kyungwha Park, Hui-Lien Tsai
″ GGA+U study of exchange interactions in a Mn5 single-molecule magnet″
8. ECMM09 Satellite Meeting on Magnetic Anisotropy, 2009, October 3-4, Wroclaw, Poland European Conference on Molecular Magnetism ECMM 2009, October 4-7, Wroclaw, Poland Chen-I Yang, Yu-Jhe Tsai, Hui-Lien Tsai, Motohiro Nakano
″ A single-chain magnet assembled by Mn6 single-molecule magnets″
9. 中國化學九十八年年會, 2009, Dec. 5-6
Yin-Ji Li (李垠輯), Kai-Hung Cheng (鄭凱鴻), Chen-I Yang (楊振宜), Hui-Lien Tsai (蔡惠蓮)
″ The Magnetic Properties of [Mn3O(R-salox)3(py)3(ClO4)] [R=Me, Et, Ph] ″ 10. 中國化學九十八年年會, 2009, Dec. 5-6
Shao-Po Hung (洪紹博), Chen-I Yang (楊振宜), Gene-Hsiang Lee (李錦祥), Hui-Lien Tsai. (蔡惠 蓮)
″ Coordinational Manganese polymers with magnetic relaxation behavior″
3. 學生畢業論文 1. 蔡育哲
五核及六核錳單分子磁鐵與六核錳單鏈磁鐵之研究 2. 鄭凱鴻
三核錳的幾何扭曲對磁性之研究
