簡易檢索 / 詳目顯示

回結果列表
研究生： 謝詩柔
Xie, Shi-Rou
論文名稱： 雙核及六核鑭系金屬團簇之合成、結構及磁性研究
Syntheses, structures, and magnetic properties of dinuclear and hexanuclear lanthanide complexes
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： 2020
畢業學年度： 108
語文別： 英文
論文頁數： 168
中文關鍵詞： 單分子磁鐵 、雙核鑭系錯合物 、六核鑭系錯合物 、希夫鹼 、β-雙酮
外文關鍵詞： single molecule magnets (SMMs), hexanuclear lanthanide complex, dinuclear lanthanide complex, Schiff base, β-diketone
相關次數： 點閱：67  下載：0 
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報

    • 本文分成兩部分，第一部份利用2-hydroxybenzohydrazide 和 1-(2-hydroxyphenyl)ethan-1-one 所形成的希夫鹼與Ln(III)金屬離子反應得到一系列4f 雙核金屬錯合物 [Ln2(L)2(NO3)2(DMF)4] (Ln = Gd (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6))，利用單晶X 光繞射儀鑑定其結構。從直流磁化率(Direct current magnetic susceptibility, dc)測量顯示化合物1-6金屬離子間存在弱的反鐵磁性(antiferromagnetic)作用力。從交流磁化率(Alternating current magnetic susceptibility, ac)測量發現3 (Dy)在零場下具有單分子磁鐵的行為，其磁異向能(Ueff)為39.9 K且5(Er)和6 (Yb)在外加場下有磁緩的現象發生，其磁異向能(Ueff)分別為36.9 K和20.0 K。此外，1 (Gd)在溫度2.5 K 並外加7 T的磁場時，有較高的磁熵變化量(27.28 J Kg-1 K-1)。第二部分利用1-(2-hydroxyphenyl)-3-phenylpropane-1,3-dione(H2ppo)與Ln(III)金屬離子反應得到4f六核金屬錯合物[Ln6(μ3-OH)2(ppo)6(NO3)4(MeOH)6(H2O)2]·2CH2Cl2·2MeOH·xH2O (Ln = Gd (9), x = 4; Dy (10), x = 3)，並藉由單晶X 光繞射儀鑑定其結構。從直流磁化率(Direct current magnetic susceptibility, dc)測量顯示化合物9和10金屬離子間存在反鐵磁性(antiferromagnetic)的作用力。從交流磁化率(Alternating current magnetic susceptibility, ac)測量發現10 (Dy)在外加場下具有磁緩的現象發生，其磁異向能(Ueff)為33.4 K。此外，9 (Gd)在溫度2.5 K 並外加7 T的磁場時，有31.09 J Kg-1 K-1的磁熵變化量。

    This work contains two parts. For the first part, a series of isostructural dinuclear [Ln2(L)2(NO3)2(DMF)4] (Ln = Gd (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6)) complexes using the Schiff base ligand (H2L = 2-hydroxy-N′-[1-(2-hydroxyphenyl)ethylidene]benzohydrazide) to react with Ln(III) metal ions. The structures of these complexes were determined by single-crystal X-ray diffraction. Structural studies show that the metal centers in complexes are bridged by two μ2-phenoxo oxygen atoms from two Schiff base ligands, leading to a Dy2(μ-O)2 core, and the Dy ions display distorted spherical tricapped trigonal prism geometry with a coordination number of 9. Direct current (dc) magnetic susceptibility measurement reveals the presence of intramolecular weak antiferromagnetic interaction in complexes 1-6. Alternating current (ac) magnetic susceptibility for complex 3 (Dy) exhibits slow relaxation of the magnetization under zero field, indicating single-molecule magnet (SMM) behavior with an energy barrier of 39.9 K. For complexes 5 (Er) and 6 (Yb), they showed a slow magnetic relaxation in an applied field on ac data. The energy barrier for complexes 5 (Er) (under 3.5 kOe) and 6 (Yb) (under 1.5 kOe) were determined to be 36.9 K and 20.0 K. In addition, the large magnetic entropy change (-∆Sm) of 1 (Gd) was estimated to be 27.28 J Kg-1 K-1 at 2.5 K and 7 T.
    For the second part, the hexanuclear lanthanide complexes [Ln6(μ3-OH)2(ppo)6(NO3)4(MeOH)6(H2O)2]·2CH2Cl2·2MeOH·xH2O (Ln = Gd (9), x = 4; Dy (10), x = 3) were synthesized from the reaction of 1-(2-hydroxyphenyl)-3-phenylpropane-1,3-dione (H2ppo) and Ln(III) metal ions. The structures of these complexes were determined by single-crystal X-ray diffraction. Direct current (dc) magnetic susceptibility measurement reveals the presence of intramolecular antiferromagnetic interaction in complexes 9 (Gd) and 10 (Dy). Alternating current (ac) magnetic susceptibilities for complex 10 (Dy), was measured and no maximum signal was observed below 10.0 K, which indicates the existence of the quantum tunneling (QTM) magnetization process. Complex 10 (Dy) showed a slow magnetic relaxation in 2.5 kOe fields based on ac data with an energy barrier of 33.4 K. Also, the magnetic entropy change (-∆Sm) of 9 (Gd) was estimated to be 31.09 J Kg-1 K-1 at 2.5 K and 7 T.

    中文摘要 I Abstract II 誌謝 IV List of table VII Lists of figures IX Chapter 1 1 I. Introduction 2 II. Experimental section 10 II.1. Synthesis 10 II.1.1. Synthesis of [Gd2(L)2(NO3)2(DMF)4] (1) 10 II.1.2. Synthesis of [Ln2(L)2(NO3)2(DMF)4] (Ln = Tb (2), Dy (3), Ho (4), Er (5), Yb (6)) 11 II.2. X-ray crystallography 13 II.3. Physical measurements 22 III. Results and discussion 23 III.1. Synthesis 23 III.2. Crystal Structure 24 III.3. Magnetic properties 31 III.3.1. DC magnetic susceptibility measurements 31 III.3.2. Field dependence of magnetization measurements 35 III.3.3. Magnetocaloric effect (MCE) 42 III.3.4. Dynamitic magnetic measurements 45 III.3.5. MAGELLAN calculation and structural comparison 76 VI. Conclusion 80 Chapter 2 82 I. Introduction 83 II. Experimental section 93 II.1. Synthesis 93 II.1.1. Synthesis of ligand H2ppo (H2ppo = 1-(2-hydroxyphenyl)-3-phenylpropane-1,3-dione) 93 II.1.2. Synthesis of [Ln6(μ3-OH)2(ppo)6(NO3)4(MeOH)6(H2O)2]·2CH2Cl2·2MeOH·xH2O (Ln = Gd (9), x = 4; Dy (10), x = 3) 94 II.2. X-ray crystallography 96 II.3. Physical measurements 100 III. Results and discussion 101 III.1. Synthesis 101 III.2. Crystal Structure 104 III.3. Magnetic properties 118 III.3.1. DC magnetic susceptibility measurements 118 III.3.2. Field dependence of magnetization measurements 123 III.3.3. Magnetocaloric effect (MCE) 126 III.3.4. Dynamitic magnetic measurements 129 III.3.5. MAGELLAN calculation and structural comparison 137 VI. Conclusion 142 References 144 Appendix 161

    1. Feltham, H. L. C.; Brooker, S. Review of purely 4f and mixed-metal nd-4f single-molecule magnets containing only one lanthanide ion. Coord. Chem. Rev. 2014, 276, 1-33.
    2. Sessoli, R.; Tsai, H.-L.; Schake, A. R.; Wang, S.; Vincent, J. B.; Foiling, K.; Gatteschi, D.; Christou, G.; Hendrickson, D. N. High-spin molecules: [Mn12O12(O2CR)16(H2O)4]. J. Am. Chem. Soc. 1993, 115, 1804-1816.
    3. Ishikawa, N.; Sugita, M.; Ishikawa, T.; Koshihara, S.-Y.; Kaizu, Y. Lanthanide double-decker complexes functioning as magnets at the single-molecular level. J. Am. Chem. Soc. 2003, 125, 8694-8695.
    4. Rinehart, J. D.; Long, J. R. Exploiting single-ion anisotropy in the design of f-element single-molecule magnets. Chem. Sci. 2011, 2, 2078–2085.
    5. Ding, Y. S.; Chilton, N. F.; Winpenny, R. E. P.; Zheng, Y.-Z. On Approaching the limit of molecular magnetic anisotropy: a near-perfect pentagonal bipyramidal dysprosium(III) single-molecule magnet. Angew. Chem. Int. Ed. 2016, 55, 16071-16074.
    6. Goodwin, C. A. P.; Ortu, F.; Reta, D.; Chilton, N. F.; Mills, D. P. Molecular magnetic hysteresis at 60 kelvin in dysprosocenium. Nature 2017, 548, 439-442.
    7. Guo, F.-S.; Day, B. M.; Chen, Y.-C.; Tong, M.-L.; Mansikkamäki, A.; Layfield, R. A. A Dysprosium metallocene single-molecule magnet functioning at the axial limit. Angew. Chem. Int. Ed. 2017, 56, 11445-11449.
    8. Guo, F.-S.; Day, B. M.; Chen, Y.-C.; Tong, M.-L.; Mansikkamäki, A.; Layfield, R. A. Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet. Science 2018, 362, 1400–1403
    9. Xie, S.-F.; Huang, L.-Q.; Zhong, L.; Lai, B.-L.; Yang, M.; Chen, W.-B.; Zhang, Y.-Q.; Dong, W. Structures, single-molecule magnets, and fluorescent properties of four dinuclear lanthanide complexes based on 4-Azotriazolyl-3-hydroxy-2-naphthoic acid. Inorg. Chem. 2019, 58, 5914-5921.
    10. Zhong, L.; Chen, W.-B.; Li, X.-H.; OuYang, Z. J.; Yang, M.; Zhang, Y.-Q.; Gao, S.; Dong, W. Four dinuclear and one-dimensional-chain dysprosium and terbium complexes based on 2-hydroxy-3-methoxybenzoic acid: structures, fluorescence, single-molecule-magnet, and Ab Initio investigation. Inorg. Chem. 2020, 59, 4414-4423.
    11. Liu, J.-L.; Chen, Y.-C.; Tong, M.-L. Symmetry strategies for high performance lanthanide-based single-molecule magnets. Chem. Soc. Rev. 2018, 47, 2431-2453.
    12. Rinehart, J. D.; Fang, M.; Evans, W. J.; Long, J. R. Strong exchange and magnetic blocking in N23--radical-bridged lanthanide complexes. Nat. Chem. 2011, 3, 538-542.
    13. Guo, Y.-N.; Xu, G.-F.; Wernsdorfer, W.; Ungur, L.; Guo, Y.; Tang, J.; Zhang, H.-J.; Chibotaru, L. F.; Powell, A. K. Strong axiality and Ising exchange interaction suppress zero-field tunneling of magnetization of an asymmetric Dy2 single-molecule magnet. J. Am. Chem. Soc. 2011, 133, 11948-11951.
    14. Liu, J.-L.; Chen, Y.-C.; Guo, F.-S.; Tong, M.-L. Recent advances in the design of magnetic molecules for use as cryogenic magnetic coolants. Coord. Chem. Rev. 2014, 281, 26-49.
    15. Yu, H.; Cao, J.-M.; Zhang, J.-R.; Li, R.-C.; Cheng, Y.; Yang, C.; Hou, Y.-L.; Fang, M. Single molecule magnet behavior and magnetic refrigeration of four tetranuclear lanthanide (Ln = GdIII, TbIII, DyIII) clusters. New. J. Chem. 2019, 43, 19429-19436.
    16. Anastasiadis, N. C.; Kalofolias, D. A.; Philippidis, A.; Tzani, S.; Raptopoulou, C. P.; Psycharis, V.; Milios, C. J.; Escuer, A.; Perlepes, S. P. A family of dinuclear lanthanide(III) complexes from the use of a tridentate Schiff base. Dalton Trans. 2015, 44, 10200-10209.
    17. Sun, O.; Sun, W.; Chen, P.; Gao, T.; Li, H.; Li, G.; Hou, G.; Yan, P. Observation of single-molecule magnetic behavior in dinuclear Schiff base dysprosium(III) complex. Synth. Met. 2016, 211, 142-146.
    18. Wang, W.-M.; Wang, S.-Y.; Zhang, H.-X.; Zhao, B.; Zou, J.-Y.; Gao, H.-L.; Cui, J.-Z. Single-molecule magnet behavior of a dinuclear dysprosium compound constructed by 8-hydroxyquinoline Schiff base and β-diketonate ligands. Inorganica Chim. Acta 2016, 439, 106-110.
    19. Liu, P.; Li, C.; Yuan, W.-J. Modulating dynamic magnetic behaviors of dysprosium(III) dinuclear compounds based on a Schiff base-like ligand by using two different β-diketone coligands. Inorganica Chim. Acta 2019, 490, 1-5.
    20. Li, X.-H.; Li, M.; Gao, N.; Wei, H.-Y.; Hou, Y.-L.; Wu, Z.-L. Solvent-driven structures and slow magnetic relaxation behaviors of dinuclear dysprosium clusters. Inorganica Chim. Acta 2020, 500, 1-6.
    21. Wang, W.-M.; Zhao, X.-Y.; Qiao, H.; Bai, L.; Han, H.-F.; Fang, M.; Wu, Z.-L.; Zou, J.-Y. Modulating the single-molecule magnet behaviour in phenoxo-O bridged Dy2 systems via subtle structural variations. J. Solid State Chem.2017, 253, 154-160.
    22. Fang, M.; Chen, Y.-Y.; Shao, L.-J.; Shi, T.-X.; Yu, H.; Li, P.-F.; Wu, Z.-L.; Wang, W.-M. Structures, luminescent and magnetic properties of three dinuclear lanthanide complexes: dysprosium compound displaying slow magnetic relaxation. Polyhedron 2019, 157, 530-535.
    23. Zhang, K.; Wang, Y.-Y. A dinuclear dysprosium single-molecule magnet constructed by o-vanillin Schiff base ligand: Magnetic properties and solution behaviour. Inorg. Chem. Commun. 2017, 76, 103-107.
    24. Chien, Y.-L.; Chang, M.-W.; Tsai, Y.-C.; Lee, G.-H.; Sheu, W.-S.; Yang, E.-C. New salen-type dysprosium(III) double-decker and triple-decker complexes. Polyhedron 2015, 102, 8-15.
    25. Nie, Y.-Y.; Wang, W.-M.; Chu, X.-Y.; Chen, H.-M.; Huang, S.-X.; Liu, Z.; Cui, J.-Z.; Gao, H.-L. Near-infrared luminescence and solvent modulation of the magnetic relaxation behavior of dinuclear lanthanide complexess. Polyhedron 2018, 151, 537-544.
    26. Wu, D.-F.; Shen, H.-Y.; Chang, W.-J.; Zhao, L.-H.; Cui, J.-Z.; Gao, H.-L. Modulating the magnetization dynamics of rare earth complexes by structural regulation utilizing different solvents. Polyhedron 2019, 159, 43-53.
    27. Zhang, K.; Guo, F.-S.; Wang, Y.-Y. Synthesis, crystal structure and magnetic properties of a dinuclear dysprosium single-molecule magnet. Inorg. Chem. Commun. 2017, 76, 95-99.
    28. Wang, W. M.; Zhang, H. X.; Wang, S. Y.; Shen, H. Y.; Gao, H. L.; Cui, J. Z.; Zhao, B. Ligand field affected single-molecule magnet behavior of lanthanide(III) dinuclear complexes with an 8-Hydroxyquinoline Schiff base derivative as bridging ligand. Inorg. Chem. 2015, 54, 10610-10622.
    29. Mukherjee, S.; Lu, J.; Velmurugan, G.; Singh, S.; Rajaraman, G.; Tang, J.; Ghosh, S. K. Influence of tuned linker functionality on modulation of magnetic properties and relaxation dynamics in a family of six isotypic Ln2 (Ln = Dy and Gd) complexes. Inorg. Chem. 2016, 55, 11283-11298.
    30. Zhang, L.; Zhang, Y.-Q.; Zhang, P.; Zhao, L.; Guo, M.; Tang, J. single-molecule magnet behavior enhanced by synergic effect of single-ion anisotropy and magnetic interactions. Inorg. Chem. 2017, 56, 7882-7889.
    31. Yu, S.; Hu, Z.; Chen, Z.; Li, B.; Zhang, Y.-Q.; Liang, Y.; Liu, D.; Yao, D.; Liang, F. Two Dy(III) single-molecule magnets with their performance tuned by Schiff base ligands. Inorg. Chem. 2019, 58, 1191-1200.
    32. Zhang, L.; Yang, P.-P.; Li, L.-F.; Hu, Y.-Y.; Gao, Y.; Tao, J. A series of Salen‐type homodinuclear lanthanide complexes and their slow magnetic relaxation in Dy2 and Ho2. Appl Organometal Chem. 2020, 34, 1-11.
    33. Qin, Y.; Zhang, H.; Sun, H.; Pan, Y.; Ge, Y.; Li, Y.; Zhang, Y.-Q. Two series of fomodinuclear lanthanide complexes: greatly enhancing energy barriers through tuning terminal solvent ligands in Dy2 single-molecule magnets. Chem. Asian. J. 2017, 12, 2834-2844.
    34. Ge, Y.; Li, D.; Wang, G.; Cui, Y.; Najib, M. S.; Li, Y.; Wang, B.-L. Single-molecule magnetism in three Dy2 complexes from the use of a pentadentate Schiff base ligand and different benzoates. Chem. Asian. J. 2019, 14, 2846-2852.
    35. Zhao, L.; Wu, J.; Ke, H.; Tang, J. Three dinuclear lanthanide(III) compounds of a polydentate Schiff base ligand: slow magnetic relaxation behaviour of the DyIII derivative. CrystEngComm. 2013, 15, 5301-5306.
    36. Ke, H.; Zhang, S.; Li, X.; Wei, Q.; Xie, G.; Wang, W.; Chen, S. A Dy2 single-molecule magnet with benzoate anions and phenol-O- bridging groups. Dalton Trans. 2015, 44, 21025-21031.
    37. Wang, S.-Y.; Wang, W.-M.; Zhang, H.-X.; Shen, H.-Y.; Jiang, L.; Cui, J.-Z.; Gao, H.-L. Seven phenoxido-bridged complexes encapsulated by 8-hydroxyquinoline Schiff base derivatives and β-diketone ligands: single-molecule magnet, magnetic refrigeration and luminescence properties. Dalton Trans. 2016, 45, 3362-3371.
    38. Wang, W.-M.; Wang, S.-Y.; Zhang, H.-X.; Shen, H.-Y.; Zou, J.-Y.; Gao, H.-L.; Cui, J.-Z.; Zhao, B. Modulating single-molecule magnet behaviour of phenoxo-O bridged lanthanide(III) dinuclear complexes by using different β-diketonate coligands. Inorg. Chem. Front. 2016, 3, 133-141.
    39. Zhang, J.; Zhang, H.; Chen, Y.; Zhang, X.; Li, Y.; Liu, W.; Dong, Y. A series of dinuclear lanthanide complexes with slow magnetic relaxation for Dy2 and Ho2. Dalton Trans. 2016, 45 , 16463-16470.
    40. Qin, Y.; Jing, Y.; Ge, Y.; Liu, W.; Li, Y.; Zhang, Y.-Q. Enhanced energy barriers triggered by magnetic anisotropy modulation via tuning the functional groups on the bridging ligands in Dy2 single-molecule magnets. Dalton Trans. 2018, 47, 15197-15205.
    41. Yang, Z.-F.; Tian, Y.-M.; Zhang, W.-Y.; Chen, P.; Li, H.-F.; Zhang, Y.-Q.; Sun, W.-B. High local coordination symmetry around the spin center and the alignment between magnetic and symmetric axes together play a crucial role in single-molecule magnet performance. Dalton Trans. 2019, 48, 4931-4940.
    42. Ma, X.; Chen, B.; Zhang, Y.-Q.; Yang, J.; Shi, Q.; Ma, Y.; Liu, X. Enhancing single-molecule magnet behaviour through decorating terminal ligands in Dy2 compounds. Dalton Trans. 2019, 48, 12622-12631.
    43. Tian, H.; Ungur, L.; Zhao, L.; Ding, S.; Tang, J.; Chibotaru, L. F. Exchange interactions switch tunneling: a comparative experimental and theoretical study on relaxation dynamics by targeted metal ion replacement. Chem. Eur. J. 2018, 24, 9928-9939.
    44. Jiang, Z.; Sun, L.; Li, M.; Wu, H.; Xia, Z.; Ke, H.; Zhang, Y.; Xie, G.; Chen, S. Solvent-tuned magnetic exchange interactions in Dy2 systems ligated by a μ-phenolato heptadentate Schiff base. RSC Adv. 2019, 9, 39640-39648.
    45. Wei, J.-Y.; Hsu, T.-J.; Wang, C.-W.; Kuo, C.-J.; Lin, P.-H. Alternate synthetic pathway leading to isolation of a dinuclear single-molecule magnet. Eur. J. Inorg. Chem. 2018, 29, 3397-3401.
    46. Zhang, P.; Zhang, L.; Lin, S.-Y.; Xue, S.; Tang, J. Modulating magnetic dynamics of Dy2 system through the coordination geometry and magnetic interaction. Inorg.Chem. 2013, 52, 4587-4592.
    47. Long, J.; Habib, F.; Lin, P.-H.; Korobkov, I.; Enright, G.; Ungur, L.; Wernsdorfer, W.; Chibotaru, L. F.; Murugesu, M. Single-molecule magnet behavior for an antiferromagnetically superexchange-coupled dinuclear dysprosium(III) complex. J. Am. Chem. Soc. 2011, 133, 5319-5328.
    48. Habib, F.; Brunet, G.; Vieru, V.; Korobkov, I.; Chibotaru, L. F.; Murugesu, M. Significant enhancement of energy barriers in dinuclear dysprosium single-molecule magnets through electron-withdrawing effects. J. Am. Chem. Soc. 2013, 135, 13242-13245.
    49. Wang, Y.-J.; Wu, D.-F.; Gou, J.; Duan, Y.-Y.; Li, L.; Chen, H.-H.; Gao, H.-L.; Cui, J.-Z. Modulation of the properties of dinuclear lanthanide complexes through utilizing different β-diketonate co-ligands: near-infrared luminescence and magnetization dynamics. Dalton Trans. 2020, 49, 2850-2861.
    50. Zhang, K.; Guo, F.-S.; Wang, Y.-Y. Two {Dy2} single-molecule magnets formed via an in situ reaction by capturing CO2 from atmosphere under ambient conditions. Dalton Trans. 2017, 46, 1753-1756.
    51. Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr. C Struct. Chem.2015, 71, 3-8.
    52. Boudreaux, E. A.; Mulay, L. Theory and applications of molecular paramagnetism. Wily : New York, 1976; px 510p.
    53. Casanova, D.; Llunell, M.; Alemany, P.; Alvarez, S. The rich stereochemistry of eight-vertex polyhedra: a continuous shape measures study. Chem. Eur. J. 2005, 11, 1479-1494.
    54. Borrás-Almenar, J. J.; Clemente-Juan, J. M.; Coronado, E.; Tsukerblat, B. S. MAGPACK A package to calculate the energy levels, bulk magnetic properties, and inelastic neutron scattering spectra of high nuclearity spin clusters. J. Comput. Chem. 2001, 22, 985-991.
    55. Chu, X.-Y.; Zhang, H.-X.; Chang, Y.-X.; Nie, Y.-Y.; Cui, J.-Z.; Gao, H.-L. A series of Ln2 complexes based on an 8-hydroxyquinoline derivative: slow magnetization relaxation and photo-luminescence properties. New J. Chem. 2018, 42, 5688-5697.
    56. Ge, Y.; Cui, Y.; Huang, Y.; Wang, G.; Liu, W.; Li, Y.; Chen, Y. A series of dinuclear lanthanide complexes derived from a hydroxyl-rich ligand: {Dy2} exhibiting single-molecule magnet behaviour. Polyhedron 2019, 159, 64-71.
    57. Sun, O.; Chen, P.; Li, H.-F.; Gao, T.; Sun, W.-B.; Li, G.-M.; Yan, P.-F. A series of dinuclear lanthanide(III) complexes constructed from Schiff base and β-diketonate ligands: synthesis, structure, luminescence and SMM behavior. CrystEngComm. 2016, 18, 4627-4635.
    58. Tu, H.-R.; Sun, W.-B.; Li, H.-F.; Chen, P.; Tian, Y.-M.; Zhang, W.-Y.; Zhang, Y.-Q.; Yan, P.-F. Complementation and joint contribution of appropriate intramolecular coupling and local ion symmetry to improve magnetic relaxation in a series of dinuclear Dy2 single-molecule magnets. Inorg. Chem. Front. 2017, 4, 499-508.
    59. Zhang, W.-Y.; Chen, P.; Li, H.-F.; Zhang, Y.-Q.; Yan, P.-F.; Sun, W.-B. Dinuclear Dy2 single-molecule magnets: functional modulation on the bridging ligand and different relaxation performances within the single-crystal to single-crystal system. Chem. Asian J. 2018, 13, 1725-1734.
    60. Gao, F.; Wang, L.; Zhu, G.-Z.; Liu, Y.-H.; Yang, H.; Li, X.; Yang, K. Controllable syntheses and magnetic properties of novel homoleptic triple-decker lanthanide complexes. Dalton Trans. 2019, 48 , 13360-13368.
    61. Jiang, Y.; Holmberg, R. J.; Habib, F.; Ungur, L.; Korobkov, I.; Chibotaru, L. F.; Murugesu, M. Probing the structural and magnetic properties of a new family of centrosymmetric dinuclear lanthanide complexes. RSC Adv. 2016, 6, 56668-56673.
    62. Lin, P.-H.; Sun, W.-B.; Tian, Y.-M.; Yan, P.-F.; Ungur, L.; Chibotaru, L. F.; Murugesu, M. Ytterbium can relax slowly too: a field-induced Yb2 single-molecule magnet. Dalton Trans. 2012, 41, 12349-12352.
    63. Chang, Y.-X.; Wang, W.-M.; Zhang, R.-X.; Shen, H.-Y.; Zhou, X.-P.; Wang, N.-N.; Cui, J.-Z.; Gao, H.-L. Dinuclear Ln(III) complexes constructed from an 8-hydroxyquinoline Schiff base derivative with different terminal groups show differing slow magnetic relaxation. New J. Chem. 2017, 41, 6251-6261.
    64. Shen, H.-Y.; Wang, W.-M.; Bi, Y.-X.; Gao, H.-L.; Liu, S.; Cui, J.-Z. Luminescence, magnetocaloric effect and single-molecule magnet behavior in lanthanide complexes based on a tridentate ligand derived from 8-hydroxyquinoline. Dalton Trans. 2015, 44, 18893-18901.
    65. Wang, W.-M.; Ren, Y.-H.; Wang, S.; Zhang, C.-F.; Wu, Z.-L.; Zhang, H.; Fang, M. Lanthanide dinuclear complexes constructed by 8-hydroxyquinoline Schiff base showing magnetic refrigeration and slow magnetic relaxation. Inorganica Chim. Acta 2016, 453, 452-456.
    66. Wang, W.-M.; Wang, Q.; Bai, L.; Qiao, H.; Zhao, X.-Y.; Xu, M.; Liu, S.-Y.; Shi, Y.; Fang, M.; Wu, Z.-L. Lanthanide-directed fabrication of three phenoxo-O bridged dinuclear compounds showing magnetic refrigeration and single-molecule magnet behavior. Polyhedron 2018, 142, 43-48.
    67. Wu, D.-F.; Liu, Z.; Ren, P.; Liu, X.-H.; Wang, N.; Cui, J.-Z.; Gao, H.-L. A new family of dinuclear lanthanide complexes constructed from an 8-hydroxyquinoline Schiff base and β-diketone: magnetic properties and near-infrared luminescence. Dalton Trans. 2019, 48, 1392-1403.
    68. Zhang, Y.-X.; Cheng, X.-Y.; Tang, Y.-T.; Zhang, Y.-H.; Wang, S.-C.; Wei, H.-Y.; Wu, Z.-L. Two dinuclear lanthanide(III) clusters (Gd2 and Dy2) constructed by bis-(o-vanillin) Schiff base ligand exhibiting fascinating magnetic behaviors. Polyhedron 2019, 166, 23-27.
    69. Li, P.-F.; Shi, T.-X.; Chen, Y.-Y.; Shao, L.-J.; Yu, H.; Fang, M.; Wang, W.-M.; Wu, Z.-L. Structures, luminescent and magnetic properties of three dinuclear lanthanide complexes: magnetic refrigeration and single-molecule magnet behaviour. Polyhedron 2019, 158, 371-376.
    70. Li, Z.-Y.; Zhang, H.; Wang, F.-F.; Zhang, F.-L.; Zhang, C.; Zhai, B. Two series of lanthanide complexes with 4-chlorophenylacetate ligand displaying luminescence and significant magnetocaloric effect. J. Mol. Struct. 2020, 1208, 1-7.
    71. Le Roy, J. J.; Ungur, L.; Korobkov, I.; Chibotaru, L. F.; Murugesu, M. Coupling strategies to enhance single-molecule magnet properties of erbium-cyclooctatetraenyl complexes. J. Am. Chem. Soc. 2014, 136, 8003-8010.
    72. Gorczyński, A.; Kubicki, M.; Pinkowicz, D.; Pełka, R.; Patroniak, V.; Podgajny, R., The first example of erbium triple-stranded helicates displaying SMM behaviour. Dalton Trans. 2015, 44, 16833-16839.
    73. Casanovas, B.; Font-Bardía, M.; Speed, S.; El Fallah, M. S.; Vicente, R. Field-induced SMM and visible/NIR-luminescence behaviour of dinuclear LnIII complexes with 2-fluorobenzoate. Eur. J. Inorg. Chem. 2018, 18, 1928-1937.
    74. Chilton, N. F.; Collison, D.; McInnes, E. J. L.; Winpenny, R. E. P.; Soncini, A. An electrostatic model for the determination of magnetic anisotropy in dysprosium complexes. Nat. Commun. 2013, 4, 1-7.
    75. Zheng, Y.-Z.; Zhou, G.-J.; Zheng, Z.; Winpenny, R. E. P. Molecule-based magnetic coolers. Chem. Soc. Rev. 2014, 43, 1462-1475.
    76. Wang, W.-M.; Han, T.-L.; Shao, Y.-L.; Qiao, X.-Y.; Wu, Z.-L.; Wang, Q.-L.; Shi, P. F.; Gao, H.-L.; Cui, J.-Z. Butterfly-shaped tetranuclear Ln4 clusters showing magnetic refrigeration and single molecule-magnet behavior. New. J. Chem. 2018, 42, 14949-14955.
    77. Evangelisti, M.; Roubeau, O.; Palacios, E.; Camón, A.; Hooper, T. N.; Brechin, E. K.; Alonso, J. J. Cryogenic magnetocaloric effect in a ferromagnetic molecular dimer. Angew. Chem. Int. Ed. 2011, 50, 6606-6609.
    78. Peng, J.-B.; Kong, X.-J.; Zhang, Q.-C.; Orendáč, M.; Prokleška, J.; Ren, Y.-P.; Long, L.-S.; Zheng, Z.; Zheng, L.-S. Beauty, symmetry, and magnetocaloric effect-four-shell keplerates with 104 lanthanide atoms. J. Am. Chem. Soc. 2014, 136, 17938-17941.
    79. Dong, J.; Cui, P.; Shi, P.-F.; Cheng, P.; Zhao, B. Ultrastrong alkali-resisting lanthanide-zeolites assembled by [Ln60] nanocages. J. Am. Chem. Soc. 2015, 137, 15988-15991.
    80. Tong, J.-P.; Shao, F.; Chen, M.-G.; Tong, Y.-N.; Zhuang, J.-J.; Xu, X.-J.; Tao, J.; Zheng, L.-S. Syntheses, structures and magnetic properties of two Dy6 clusters based on polydentate ligands with a new topological motif. Inorg. Chem. Commun. 2016, 74, 93-97.
    81. Blagg, R. J.; Ungur, L.; Tuna, F.; Speak, J.; Comar, P.; Collison, D.; Wernsdorfer, W.; McInnes, E. J. L.; Chibotaru, L. F.; Winpenny, R. E. P. Magnetic relaxation pathways in lanthanide single-molecule magnets. Nat. Chem. 2013, 5, 673-678.
    82. Blagg, R. J.; Muryn, C. A.; McInnes, E. J. L.; Tuna, F.; Winpenny, R. E. P. Single pyramid magnets: Dy5 pyramids with slow magnetic relaxation to 40 K. Angew. Chem. Int. Ed. 2011, 50, 6530-6533.
    83. Lu, J.; Li, X.-L.; Zhu, Z.; Liu, S.; Yang, Q.; Tang, J. Linear hexanuclear helical dysprosium single-molecule magnets: the effect of axial substitution on magnetic interactions and relaxation dynamics. Dalton Trans. 2019, 48, 14062-14068.
    84. Kostakis, G. E.; Blatov, V. A.; Proserpio, D. M. A method for topological analysis of high nuclearity coordination clusters and its application to Mn coordination compounds. Dalton Trans. 2012, 41, 4634-4640.
    85. 黃湘樺, (2013)十四核錳及六核鑭系金屬簇之合成及磁性研究，國立成功大學研究所碩士論文
    86. Ke, H.; Zhao, L.; Guo, Y.; Tang, J. A Dy6 cluster displays slow magnetic relaxation with an edge-to-edge arrangement of two Dy3 triangles. Eur. J. Inorg. Chem. 2011, 27, 4153-4156.
    87. Tian, H.; Guo, Y.-N.; Zhao, L.; Tang, J.; Liu, Z. Hexanuclear dysprosium(III) compound incorporating vertex- and edge-sharing Dy3 triangles exhibiting single-molecule-magnet behavior. Inorg. Chem. 2011, 50, 8688-8690.
    88. Adhikary, A.; Sheikh, J. A.; Biswas, S.; Konar, S. Synthesis, crystal structure and study of magnetocaloric effect and single molecular magnetic behaviour in discrete lanthanide complexes. Dalton Trans. 2014, 43, 9334-9343.
    89. Das, S.; Hossain, S.; Dey, A.; Biswas, S.; Sutter, J.-P.; Chandrasekhar, V. Molecular magnets based on homometallic hexanuclear lanthanide(III) complexes. Inorg. Chem. 2014, 53, 5020-2028.
    90. Wu, L.-J.; Yang, H.; Zeng, S.-Y.; Li, D.-C.; Dou, J.-M. A family of hexanuclear lanthanide complexes with slow magnetic relaxation for Dy6 cluster. Polyhedron 2017, 129, 77-81.
    91. Liu, Z.-Y.; Zou, H.-H.; Wang, R.; Chen, M.-S.; Liang, F.-P. Structure and magnetism of two chair-shaped hexanuclear dysprosium(III) complexes exhibiting slow magnetic relaxation. RSC Adv. 2018, 8, 767-774.
    92. Zhang, Y.; Wu, J.; Shen, S.; Liu, Z.; Tang, J. Coupling Dy3 triangles into hexanuclear dysprosium(III) clusters: syntheses, structures and magnetic properties. Polyhedron 2018, 150, 40-46.
    93. Wang, W.-M.; Yue, R.-X.; Gao, Y.; Wang, M.-J.; Hao, S.-S.; Shi, Y.; Kang, X.-M.; Wu, Z.-L. Large magnetocaloric effect and remarkable single-molecule-magnet behavior in triangle-assembled LnIII6 clusters. New J. Chem. 2019, 43, 16639-16646.
    94. Baniodeh, A.; Magnani, N.; Bräse, S.; Anson, C. E.; Powell, A. K. Ligand field variations: tuning the toroidal moment of Dy6 rings. Dalton Trans. 2015, 44, 6343-6347.
    95. Tian, H.; Bao, S.-S.; Zheng, L.-M. Enlarging the ring by incorporating a phosphonate coligand: from the cyclic hexanuclear to octanuclear dysprosium clusters. Dalton Trans. 2015, 44, 14208-14212.
    96. Tian, H.; Bao, S.-S.; Zheng, L.-M. Cyclic Single-molecule magnets: from even-numbered hexanuclear to odd-numbered heptanuclear dysprosium clusters. Eur. J. Inorg. Chem. 2016, 19, 3184-3190.
    97. Langley, S. K.; Moubaraki, B.; Forsyth, C. M.; Gass, I. A.; Murray, K. S. Structure and magnetism of new lanthanide 6-wheel compounds utilizing triethanolamine as a stabilizing ligand. Dalton Trans. 2010, 39, 1705-1708.
    98. Ungur, L.; Langley, S. K.; Hooper, T. N.; Moubaraki, B.; Brechin, E. K.; Murray, K. S.; Chibotaru, L. F. Net toroidal magnetic moment in the ground state of a {Dy6}-triethanolamine ring. J. Am. Chem. Soc. 2012, 134, 18554-18557.
    99. Joarder, B.; Mukherjee, S.; Xue, S.; Tang, J.; Ghosh, S. K. Structures and magnetic properties of two analogous Dy6 wheels with electron-donation and -withdrawal effects. Inorg. Chem. 2014, 53, 7554-7560.
    100. Langley, S. K.; Vignesh, K. R.; Gupta, T.; Gartshore, C. J.; Rajaraman, G.; Forsyth, C. M.; Murray, K. S. New examples of triangular terbium(III) and holmium(III) and hexagonal dysprosium(III) single molecule toroics. Dalton Trans. 2019, 48, 15657-15667.
    101. Lu, J.; Montigaud, V.; Cador, O.; Wu, J.; Zhao, L.; Li, X.-L.; Guo, M.; Le Guennic, B.; Tang, J. Lanthanide(III) hexanuclear circular helicates: slow magnetic relaxation, toroidal arrangement of magnetic moments, and magnetocaloric effects. Inorg. Chem. 2019, 58 , 11903-11911.
    102. Mudring, A.-V.; Timofte, T.; Babai, A. Cluster-type basic lanthanide iodides [M6(µ6-O)(µ3-OH)8(H2O)24]I8(H2O)8 (M = Nd, Eu, Tb, Dy). Inorg. Chem. 2006, 45, 5162−5166.
    103. Tong, Y.-Z.; Wang, Q.-L.; Yang, G.; Yang, G.-M.; Yan, S.-P.; Liao, D.-Z.; Cheng, P. Hydrolytic synthesis and structural characterization of five hexanuclear oxo-hydroxo lanthanideclusters. CrystEngComm. 2010, 12, 543-548.
    104. Hou, Y.-L.; Xiong, G.; Shi, P.-F.; Cheng, R.-R.; Cui, J.-Z.; Zhao, B. Unique (3,12)-connected coordination polymers displaying high stability, large magnetocaloric effect and slow magnetic relaxation. Chem. Commun. 2013, 49, 6066-6068.
    105. Anwar, M. U.; Dawe, L. N.; Tandon, S. S.; Bunge, S. D.; Thompson, L. K. Polynuclear lanthanide (Ln) complexes of a tri-functional hydrazone ligand--mononuclear (Dy), dinuclear (Yb, Tm), tetranuclear (Gd), and hexanuclear (Gd, Dy, Tb) examples. Dalton Trans. 2013, 42, 7781-7794.
    106. Biswas, S.; Das, S.; Acharya, J.; Kumar, V.; van Leusen, J.; Kögerler, P.; Herrera, J. M.; Colacio, E.; Chandrasekhar, V. Homometallic DyIII complexes of varying nuclearity from 2 to 21: synthesis, structure, and magnetism. Chem. Eur. J. 2017, 23, 5154-5170.
    107. Wang, Y.-F.; Wang, W.-M.; Sun, H.-F.; Wang, W.-T.; Wang, M.-Y.; Tang, Y.-T.; Wu, Z.-L. A new planar hexanuclear dysprosium cluster exhibiting slow magnetic relaxation features. Z. Anorg. Allg. Chem. 2019, 645, 1291-1295.
    108. Tian, H.; Wang, M.; Zhao, L.; Guo, Y.-N.; Guo, Y.; Tang, J.; Liu, Z. A discrete dysprosium trigonal prism showing single-molecule magnet behaviour. Chem. Eur. J. 2012, 18, 442-445.
    109. Guo, Y.-N.; Chen, X.-H.; Xue, S.; Tang, J. Molecular assembly and magnetic dynamics of two novel Dy6 and Dy8 aggregates. Inorg. Chem. 2012, 51, 4035-4042.
    110. Hussain, B.; Savard, D.; Burchell, T. J.; Wernsdorfer, W.; Murugesu, M. Linking high anisotropy Dy3 triangles to create a Dy6 single-molecule magnet. Chem. Commun.2009, 9, 1100-1102.
    111. Hewitt, I. J.; Tang, J.; Madhu, N. T.; Anson, C. E.; Lan, Y.; Luzon, J.; Etienne, M.; Sessoli, R.; Powell, A. K. Coupling Dy3 triangles enhances their slow magnetic relaxation. Angew. Chem. Int. Ed. 2010, 49, 6352-6356.
    112. Lin, S.-Y.; Wernsdorfer, W.; Ungur, L.; Powell, A. K.; Guo, Y.-N.; Tang, J.; Zhao, L.; Chibotaru, L. F.; Zhang, H.-J. Coupling Dy3 triangles to maximize the toroidal moment. Angew. Chem. Int. Ed. 2012, 51 , 12767-12771.
    113. Lin, S.-Y.; Wu, J.; Xu, Z. The effect of additional methyl on the magnetic relaxation and toroidal moment of Dy6 complex. RSC Adv. 2017, 7, 47520-47526.
    114. Bi, Y.-F.; Xu, G.-C.; Liao, W.-P.; Du, S.-C.; Deng, R.-P.; Wang, B.-W. Calixarene-supported hexadysprosium cluster showing single molecule magnet behavior. Sci. China. Chem. 2012, 55, 967-972.
    115. Zhang, H.; Liu, R.; Zhang, J.; Li, Y.; Liu, W.; Dong, Y. Five rare μ4-O-centered Ln6 clusters with single-molecule magnet behavior for Dy6. Chem. Asian. J. 2017, 12, 507-514.
    116. Lu, J.; Li, X.-L.; Jin, C.; Yu, Y.; Tang, J. Dysprosium-based linear helicate clusters: syntheses, structures, and magnetism. New J. Chem. 2020, 44, 994-1000.
    117. Langley, S. K.; Moubaraki, B.; Murray, K. S. Magnetic properties of hexanuclear lanthanide(III) clusters incorporating a central mu6-carbonate ligand derived from atmospheric CO2 fixation. Inorg. Chem. 2012, 51, 3947-3949.
    118. Mukherjee, S.; Chaudhari, A. K.; Xue, S.; Tang, J.; Ghosh, S. K. An asymmetrically connected hexanuclear DyIII6 cluster exhibiting slow magnetic relaxation. Inorg. Chem. Commun. 2013, 35, 144-148.
    119. She, S.; Chen, Y.; Zaworotko, M. J.; Liu, W.; Cao, Y.; Wu, J.; Li, Y. Synthesis, structures and magnetic properties of a family of nitrate-bridged octanuclear [Na2Ln6] (Ln = Dy, Tb, Gd, Sm) complexes. Dalton Trans. 2013, 42, 10433-10438.
    120. Levine, B. R.; Sneed, J. K. The synthesis of new β-diketones. J. Am. Chem. Soc. 1951, 73, 4478.
    121. Wang, R.; Han, J.; Li, C.; Zhang, J.; Liang, Y.; Wang, T.; Zhang, Z. One-pot synthesis of 3-fluoroflavones via 1-(2-hydroxyphenyl)-3-phenylpropane-1,3-diones and selectfluor at room temperature. Org. Biomol. Chem. 2018, 16, 2479-2488.
    122. Wang, C.; Lin, S.-Y.; Wu, J.; Yuan, S.-W.; Tang, J. Employment of triketones to construct a dysprosium(III) single-molecule magnet. Dalton Trans. 2015, 44, 4648-4654.
    123. Hutchings, A.-J.; Habib, F.; Holmberg, R. J.; Korobkov, I.; Murugesu, M. Structural rearrangement through lanthanide contraction in dinuclear complexes. Inorg. Chem. 2014, 53, 2102-2112.

    無法下載圖示 校內：2025-08-20公開
    校外：不公開
    電子論文尚未授權公開，紙本請查館藏目錄
    QR CODE