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研究生: 劉名軒
Liu, Ming-Hsuan
論文名稱: 多核錳及鏑分子磁鐵之合成及磁性研究
Syntheses and magnetic studies of polynuclear manganese and dysprosium molecular magnets
指導教授: 蔡惠蓮
Tsai, Hui-Lien
學位類別: 碩士
Master
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2012
畢業學年度: 100
語文別: 英文
論文頁數: 129
中文關鍵詞: 單分子磁鐵水楊醛肟直流磁化率交流磁化率單晶X-ray繞射
外文關鍵詞: Single-Molecule Magnet, salicylaldoxime, DC Susceptibility, AC susceptibility, single crystal X-ray crystallography
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  • 本論文分三部分,第一部分以含有水楊醛肟(salicylaldoxime, H2sao)衍生物R-H2sao的MnIII三核錳錯化合物和水楊酸(salicylic acid)配位基反應得到不對稱六核錳團簇化合物[Mn6O2(R-sao)6(Sal)2(MeCN)2]∙3MeCN (R = Et (1), Me (2))。皆利用單晶X-ray繞射確認其結構。從直流磁化率(direct current susceptibility, DC)測量顯示化合物1的基態S = 6及化合物2的基態S = 4。從交流磁化率(alternating current susceptibility, AC)與磁滯迴路(hysteresis loop)的量測,顯示化合物1和2具有單分子磁鐵(single-molecule magnet)的行為。第二部分以苯甲酸根的四核錳錯化合物和三核錳錯化合物及水楊酸在乙腈的環境下反應,得到具高對稱性結構的七核錳錯化合物(NBun4)[Mn7O2(Et-sao)6(O2CPh)6]∙3H2O (3∙3H2O),也利用單晶X-ray繞射確認其結構。由直流磁化率和縮減磁化率(Reduced susceptibility)的量測結果,顯示化合物3的基態是 S = 6。從交流磁化率的測量顯示具有磁緩現象。第三部分以三核錳錯化合物硝酸鏑金屬鹽和含吡啶的β-二酮類配位基(HL = 1-(naphthalen-2-yl)-3-(pyridin-2-yl)propane-1,3-dione)在甲醇及二氯甲烷混和溶劑下反應,得到三核鏑金屬簇化合物[Dy3(OH)2(L)3(NO3)4(MeOH)(H2O)]•2MeOH•2CH2Cl2 (4•2MeOH•2CH2Cl2),單晶X-ray繞射鑑定出結構。其磁性性質量測,交流磁化率的數據顯示有單分子磁鐵的行為。

    This thesis consists of three parts. The first part, the complexes, [Mn6O2(R-sao)6(Sal)2(MeCN)2]∙3MeCN (R = Et (1), Me (2)), were synthesized from the reactions of [Mn3O(R-sao)3(MeOH)3(ClO4)] and salicylic acid generate two twisted and rotated [MnIII3(-O)]7+ units to construct the Mn6-oxime cluster. The structures of these complexes are determined by single crystal X-ray crystallography. The data of direct current susceptibility indicate the spin ground state of S = 6 of compound 1 and the spin ground state of S = 4 of compound 2. The data of alternating current susceptibility and hysteresis loops suggest the compounds 1 and 2 exhibit the single-molecule magnet behavior. The second part, the reaction of [Mn4] and [Mn3] complexes with salicylic acid in the environment of acetonitrile products the high-symmetric [Mn7] complex, (NBun4)[Mn7O2(Et-sao)6(O2CPh)6]∙3H2O (3∙3H2O), confirmed by single crystal X-ray crystallography. The data of DC and reduced susceptibility measurements agree with the spin ground state of S = 6 of compound 3. The out-of-signals of AC susceptibility reveal the slow relaxation of magnetization. The third part, the [Mn3] complex and dysprosium(III) nitrate hydrate reacted with HL ligand (HL = 1-(naphthalen-2-yl)-3-(pyridin-2-yl)propane-1,3-dione) in the mixed-solvent of MeOH and CH2Cl2 to obtain the trinuclear dysprosium complex, [Dy3(OH)2(L)3(NO3)4(MeOH)(H2O)]•2MeOH•2CH2Cl2 (4•2MeOH•2CH2Cl2). The structure of the complex is also determined by single crystal X-ray crystallography. The various magnetic properties of complex 4 were studied. The AC susceptibility measurements indicate complex 4 exhibits the SMM behavior.

    Abstract in Chinese 中文摘要 I Abstract II Acknowledgement III Contents IV List of Tables VI List of Figures VIII Abbreviations & Ligand Diagram XV Chapter 1 Single-Molecule Magnets: [Mn6O2(R-sao)6(Sal)2(MeCN)2]∙3MeCN (R=Et(1), Me(2)) 1 I. Introduction 2 II. Experimental Section 15 II. 1. Synthesis 15 II. 2. X-Ray Crystallography 16 II. 3. Physical Measurements 17 III. Results and Discussion 19 III. 1. Description of Structures 19 III. 2. Magnetic properties 31 IV. Conclusion 48 V. References 57 Chapter 2 A Single-Molecule Magnet: (NBun4)[Mn7O2(Et-sao)6(O2CPh)6]∙3H2O (3∙3H2O) 61 I. Introduction 62 II. Experimental Section 67 II. 1. Synthesis 67 II. 2. X-Ray Crystallography 68 II. 3. Physical Measurements 68 III. Results and Discussion 69 III. 1. Description of Structure 69 III. 2. Magnetic Properties 72 IV. Conclusion 79 V. References 82 Chapter 3 A Single-Molecule Magnet: [Dy3(OH)2(L)3(NO3)4(MeOH)(H2O)]•2MeOH•2CH2Cl2 (4•2MeOH•2CH2Cl2) 86 I. Introduction 87 II. Experimental Section 94 II. 1. Synthesis 94 II. 2. X-Ray Crystallography 96 II. 3. Physical Measurements 97 III. Results and Discussion 98 III. 1. Description of Structure 98 III. 2. Magnetic Properties 103 IV. Conclusion 106 V. References 117 Appendix ………………………………………………………………………………….… 122

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