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| ???org.dspace.app.webui.jsptag.ItemTag.dcfield??? | Value | Language |
|---|---|---|
| dc.contributor.advisor | 王瑜(Yu Wang) | |
| dc.contributor.author | Hsin-Yi Lin | en |
| dc.contributor.author | 林欣怡 | zh_TW |
| dc.date.accessioned | 2021-06-12T18:22:01Z | - |
| dc.date.available | 2009-08-28 | |
| dc.date.copyright | 2007-08-28 | |
| dc.date.issued | 2007 | |
| dc.date.submitted | 2007-08-19 | |
| dc.identifier.citation | 1. B. J. Wallar and J. D. Lipscomb, Chem. Rev., 1996, 96,
2625. 2. L. Que, Jr. and R. Y. N. Ho, Chem. Rev., 1996, 96, 2607. 3. S. J. Lippard, Angew. Chem., Int. Ed. Engl., 1988, 27, 344. 4. P. M. Harrison and P. Arosio, Biochem. Biophys. Acta, 1996, 1275,161 5. McCusker, J. K.; Christmas, C. A.; Hagen, P.M.; Chadha, R.K.;Harvey, D. F.; Hendrickson, D. N. J. Am. Chem.Soc. 1991, 113, 6114. 6. Delfs, C.; Gatteschi, D.; Pardi, L.; Sessoli,R.; Wieghardt, K.; Hanke, D.Inorg. Chem. 1993, 32, 3099. 7. Wemple, M.W.; Coggin, D. K.; Vincent, J. B.; McCusker, J. K.; Streib, W. E.;Huffman, J. C.; Hendrickson, D. N.; Christou, G. J. Chem. Soc.,Dalton Trans. 1998, 719. 8. Tanase, T.; Inoue, C.; Ota, E.; Yano, S.;Takahashi, M.; Takeda, M.Inorg. Chim. Acta 2000, 297, 18.C. A.; Wang, X.; Zhou, H. Inorg.Chim. Acta 1997, 266, 91. 9. Murch, B. P.; Boyle, P. D.; Que, L., Jr. J. Am. Chem. Soc. 1985,107, 6728. 10. Cotton, F. A.; Daniels, L. M.; Maloney, D. J.; Murillo, C. A, Inorg.Chim. Acta 1996, 252, 293. 11. Saalfrank, R. W.; Burak, R.; Breit, A.; Stalke, D.; Herbst-Irmer, R.;Daub, J.; Porsch, M.; Bill, E.; Mu¨ ther, M.; Trautwein, A. X. Angew.Chem., Int. Ed. Engl. 1994, 33, 1621. 12. Barra, A. L.; Caneschi, A.; Cornia, A.; de Biani, F.; Fabrizi; Gatteschi,D.; Sangregorio, C.; Sessoli, R.; Sorace, L. J. Am. Chem. Soc. 1999,121, 5302. 13. Thorpe, J. M.; Beddoes, R. L.; Collison, D.; Garner, C. D.; Helliwell,M.; Holmes, J. M.; Tasker, P. A. Angew. Chem., Int. Ed. Engl. 1999,38, 1119. 14. Taft, K. L.; Caneschi, A.; Pence, L. E.; Delfs, C. D.; Papaefthymiou, G.C.; Lippard, S. J. J. Am. Chem. Soc. 1993, 115, 11753. 15. Sugimoto, H.; Hayashi, Y.; Koshi, C.; Fujinami, S.; Suzuki, M.;Maeda,Y.; Uehara, A. Chem. Lett. 1996, 933. 16. Shoner, S. C.; Power, P. P. Inorg. Chem. 1992, 31, 1001. 17. Mandal, S. K.; Young, V. G., Jr.;Que, L., Jr. Inorg. Chem. 2000, 39,1831. 18. Cotton, F. A.; Daniels, L. M.; Falvello, L. R.; Matonic, J. H.; Murillo,C. A.; Wang, X.; Zhou, H. Inorg. Chim. Acta 1997, 266, 91. 19. Cotton, F. A.; Daniels, L. M.; Jordan, G. T.; Murillo, C. A.; Pascual,I.Inorg. Chim. Acta 2000, 297, 6. 20. Reynolds, R. A., III; Coucouvanis, D. Inorg. Chem. 1998, 37, 170. 21. Caneschi, A.; Gatteschi, D.; Sessoli, R.; Barra, A.- L.; Brunel, L.-C.;Guillot, M. J. Am. Chem. Soc. 1991, 113, 5873. 22. Gatteschi, D.; Sessoli, R.; Cornia, A. J. Chem. Soc.,Chem. Commun. 2000, 725. 23. Godbole , M. D. ; Roubeau O.; Mills, A.M.; Kooijman, H.; Spek, A. L. ; Bouwman, E. Inorg. Chem. 2006, 45, 6713-6722 24. R. Prins, P.J.M.W.L. Birker, J.G. Haasnoot, G.C. Verschoor, J.Reedijk, Inorg. Chem. 1985, 24, 4128. 25. W.M.E. Koomen-van Oudenniel, R.A.G. de Graaff, J.G. Haasnoot,R. Prins, J. Reedijk, Inorg. Chem. 1989, 28, 1128. 26. P.J. van Koningsbruggen, J.G. Haasnoot, R.A.G. de Graaff, J. Reedijk,S. Slingerland, Acta Crystallogr., C ,1992,48,1923. 27. P.M. Slangen, P.J. van Koningsbruggen, K. Goubitz, J.G. Haasnoot, J.Reedijk, Inorg. Chem.1994,33,1121. 28. P.J. van Koningsbruggen, J.G. Haasnoot, H. Kooijman, J. Reedijk, A.L.Spek, Inorg. Chem. 1997,36, 2487. 29. Y. Garcia; P.J. van Koningsbruggen; G. Bravic; P. Guionneau; D.Chasseau; G.V. Cascarano; J. Moscovici; K. Lambert; A. Michalowicz;O. Kahn. Inorg. Chem. 1997, 36, 6357. 30. P.J. van Koningsbruggen, M.W. Gluth, V. Ksenofontov, D. Walcher,D. Schollmeyer, G. Levchenko, P. Gütlich, Inorg. Chim. Acta.,1998, 273, 54. 31. Qihua Zhao, Haifang Li, Zhida Chen, Ruibin Fang, Inorg. Chim.Acta.2002, 336, 142-146 32. F.J. Rietmeijer, G.A. van Albada, R.A.G. de Graaff, J.G. Haasnoot, J.Reedijk, Inorg. Chem.1985,24,3597. 33. G.A. van Albada, R.A.G. de Graaff, J.G. Haasnoot, J. Reedijk, Inorg. Chem.1984, 23, 1404. 34. J. F. Lee, X光吸收光譜術在觸媒特性分析上的應用, Chemistry (the Chinese Chem. Soc.),1995, 53, 280-293. 35. R.S Drago, Physical Methods for Chemists 2nd Edn., Saunders College, Florida, 1992. 36. http://www.nsrrc.org.tw/ 37. http://nano.mse.ttu.edu.tw/html/doc/Class01_Intro/4.pdf 38. 楊宗燁、林鴻明、吳泉毅與林中魁， 物理雙月刊，2001,23， 640. 39. I. J. Hsu, R. S. Liu, J. M. Chen, R. G. Liu, L. Y. Jang, J. F. Lee and K.D. M. Harris, Chem. Mater. 2000,12, 1115.pdf-38 40. A. Bianconi, X-Ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS and XANES, ed. By D. C. Koningsberger and R. Prins, John Wiley & Sons, New York, 573 (1988). 41. E. A. Stern, X-Ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS and XANES, eds. by D. C. Koningsberger and R. Prins, John Wiley & Sons, New York, 3 (1988). 42. T. Yokoyama, X-Ray Absorption Fine Structure for Catalysts and Surface, ed. by Y. Iwasawa, World Scientific, Singapore, 9 (1996). 43. D.A. Skoog and J. J. Leary, principles of instrumental analysis, Saunders Brace, Orlando, Chpater 22 (1992) 44. http://www.phys.ncku.edu.tw/modphyslab/ESR/theorem.htm 45. Rabenau, A.：Angrew. Chem. Int. Ed. Engl. 1985, 24, 1026 46. SMART V 4.043 Software for CCD Detector System; Siemens Analytical Instruments Division Madison, WI, 1995. 47. SAINT V 4.035 Software for CCD Detector System; Siemens Analytical Instruments Division Madison, WI, 1995. 48. Sheldrick, G. M. Program for the Refinement of Crystal Structure; University of Göttingen: Göttingen, Germany, 1993. 49. SHELXTL 5.03 (PC-Version), Program Liberary for Structure Solution and Molecular Graphics; Siemens Analytical Instruments Division: Madison, WI, 1995. 50. Raphael G. Raptis, Irene P. Georgakaki, and David C. R. Hockless, Angew. Chem. Int. Ed. 1999, 38,1632-1634. 51. F. A. Cotton, L. M. Daniels, L. R. Falvello, J. H. Matonic, C. A. Murillo, X. Wang, H. Zhou, Inorg. Chim.Acta,1997, 266, 91-102 52. Elisa J. Seddon, John C. Hu.man and George Christou, J. Chem. Soc., Dalton Trans., 2000, 4446–4452 53. V. S. Nair and K. S. Hagen, Inorg. Chem., 1994, 33, 185. 54. V. S. Nair and K. S. Hagen, Inorg. Chem., 1992, 31, 4048. 55. Harald K.; Bernd H.; Evan R.; Franz G.; Karl-Heinz G.; Konrad M., Physiol. Plant., 2004, 122, 95-106. 56. Donald M., Kurtz, JR., Chem. Rev. 1990, 90, 585-606. 57. Michael T. Green, J. Am. Chem. Soc. 2006, 128, 1902- 1906. 58. Helga Hummel,; Eckhard Bill,; Thomas Weyhermüller,; Karl Wieghardt, Inorg. Chim.Acta, 1999, 291, 258-265 59. Hua-Fen Hsu,; Yanhong Dong, Lijin Shu,; Victor G. Young,; Jr., and Lawrence Que, Jr., J. Am. Chem. Soc. 1999, 121, 5230-5237. 60. Sonia Taktak,; Sergey V. Kryatov,; Terry E. Haas,; Elena V. Rybak-Akimova, J. Mol. Catal. A. 2006, 259, 24-34 61. Anindya G., Filipe Tiago D. O.; Toshihiro Y.; Takanori N.; Evan S. B.; Isamu K.; Eckard M.; Alexander D. R.; Colin P. H.; Terrence J. C., J. Am. Chem. Soc. 2005, 127, 2505-2513. 62. Abhik G.; Espen T.; Hege R.; Peter R. T., Eur. J. Inorg. Chem. 2004, 4555-4560. 63. William H. A.; Stephen J. L., J. Am. Chem. Soc. 1983, 105, 4837-4838. 64. Martin N. M.; Birgit J.; Alan H.; Andrew D. B.; Christine J. M., Dalton Trans., 2004, 3396-3402. 65. William H. A.; Stephen J. L., J. Am. Chem. Soc. 1984, 106, 4632-4633. 66. Josseline J.; Gergely J.; Pierre M.; Eddy D.; Cédric R. M.; Jérôme M.; Eric R.; Emile L. B.; Eckard M.; Francis S., Inorg. Chem., 2006, 45, 6922-6927. 67. S.Yoon, S.J.Lippard, J.Am.Chem.Soc.2004,126,16692 68. S.Menage, J-B.Galey, J.Dumats, G.Hussler, M.Seite, I.G.Luneau, G.Chottard, M.Fontecave,J.Am.Chem.Soc., 1998, 120, 13370. 69. E.Vogel, S.Will, A.S.Tilling, L.Neumann, J. Lex, E.Bill, A.X.Trautwein, K.Wieghardt,Angew.Chem.,Int.Ed., 1994, 33, 731. 70. P.Chaudhuri, K.Wieghardt, B.Nuber, J.Weiss,Angew.Chem., Int.Ed.,1985, 24, 778. 71. S.Yoon, S.J.Lippard,J. Am.Chem.Soc., 2004, 126, 2666 72. W.B.Tolman, Shuncheng Liu, J.G.Bentsen, S.J.Lippard, J.Am.Chem.Soc., 1991,113,152. 73. A.A.M. Prince, S. Mylswamy, T.S. Chan, R.S. Liu, B. Hannoyer, M.Jean,C.H. Shen, S.M. Huang, J.F. Lee, G.X. Wang, Solid State Commun.2004,132,455–458 74. Max W.; Francois F.; Pierre P.; Gordon E. B.; Francois M., American Mineralogist, 2001, 86, 714–730. 75. Tami E. W.; Pierre K.; Jane G. D.; Britt H.; Keith O. H.; Edward I. S., J. Am. Chem. Soc. 1997, 119, 6297- 6314 76.Wasinger, E. C.; de Groot, F. M. F.; Hedman, B.; Hodgson, K. O.; Solomon, E. I., J. Am. Chem. Soc, 2003, 125, 12894-12906. 77. Rosalie K. H.; Erik C. W., Yi-Long Y.; Frank M. F.; F. Ann W. ;Keith O. H.; Britt H.; Edward I. S., J. Am. Chem. Soc, 2007, 129, 113-125. 78. Hongxin W.; Gang P.; Lisa M. M.; Eva M. S.; George S. J.; Mark R. C.; Stephen P. C., J. Am. Chem. Soc, 1997, 119, 4921-4928. 79. Michael J. C.; Kallol R.; Lawrence Q.; Jr, Inorg. Chem., 2006, 45, 8009-8011. 80. Chiivukula V. S.; Kyungeun O.; Yoon J. L.; Mi S. S.; Woonsup S.;Wonwoo N., Angew. Chem. Int. Ed. 2006, 45,3992-3995. 81. Leonardo D. S.; Ana M.; Wolfram M. Thomas W.; Eckhard B.;Eberhard B.; Frank N.; Karl W., J. Am. Chem. Soc, 2003, 125, 15554-15570. 82. Hyungphil C., Eckhard B., Eberhard B., Thomas W., Karl W., Inorg.Chem. 2002, 41, 5091-5099. 83. Vincent A. G., Lawrence R. G., Graeme R. H., Robert S.,Trevor W. H., Keith S. M., Boujemaa M., John D. C., J. Chem. Soc., Dalton Trans., 1998, 2341–2348. 84. Apurba K. P., Eckhard B., Eberhard B., Krzysztof C., Frank N., Thomas W., Keira S., Michael D. W., Jon A. M., Karl W., Inorganic Chemistry, 2006, 45, 443 85. Vassilios P., Catherine P. R., Athanassios K. B., Yiannis S., Michael F.,George D., and George P., Eur. J. Inorg. Chem. 2006, 3710–3723. 86. Helga H.; Eckhard B.; Thomas W.; Karl W., Inorganica Chimica Acta.,1999, 291, 258–265. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/27813 | - |
| dc.description.abstract | 具有多核性與恰當的拓樸學之特質的多核金屬簇，由於本身在基態時擁有大規模的整體自旋數值，因此有時能夠作為單分子磁鐵(single-molecule magnets , SMMs)的應用潛力。目前的研究主要是著重在以氧原子和含氮的triazole配基作為架橋配基，進一步地設計及合成出多核鐵金屬簇(polynuclear iron clusters)。 成功地合成出三個新穎多核鐵簇化合物︰
(一) [Fe4(μ4-O)(μ-OR)4(μ-dmatrz)3(NCS)6] , (μ-OR = CH3CH2O(1) ; CH3O (2)) (二) [Fe3(μ-dmatrz)4(O)(OH)(NCS)6].2H2O (3) 在第一系列鐵簇錯合物[Fe4(μ4-O)(μ-OR)4(μ-dmatrz)3(NCS)6] , (μ-OR= CH3CH2O (1) ; CH3O (2))中，這兩個鐵簇都具有相同的晶體結構(isostructure)，都是由一個氧原子連接著四個金屬鐵離子為一[Fe4O]結構單元形成四角錐狀(tetrahedral)之四核鐵簇。錯合物(1)和(2)之平均鐵金屬離子與氧之間鍵長分別為2.019(2)、2.017(2) Å；平均鐵金屬離子與氮之間鍵長分別為2.185(4)、2.194(4) Å。第二系列的錯合物(3)為一個直線形的三核鐵金屬簇，其位於中間處的鐵離子位於反轉中心上，並經由四個triazole配基以N1,N2架橋鍵結模式和兩個氧橋來連接著兩個末端的鐵離子而構築成扭曲的八面體結構(distortion octahedral)，其中間的鐵離子與氮跟氧原子之間平均鍵長分別2.155(3) 和1.896 (2) Å。除了架橋配基之外，位於末端處的鐵離子也由另外三個NCS陰離子所提供的氮原子以fac 形態鍵結而形成六配位的配位環境。 本研究中將經由電化學之循環伏安法(CV) 量測來研究其電化學性質、電子順磁共振光譜(EPR)來鑑定推斷出鐵離子所具有未成對的電子數目、X光吸收光譜(K-edge and L-edge)來決定多核鐵離子的氧化態和自旋態，並經由超導量子干涉儀的測量來探討多核鐵金屬簇的磁性現象，皆顯示鐵簇錯合物(1)、(2)和(3)都為強烈的反鐵磁作用力之磁性性質，並利用鐵之K-edge 和L-edge X光吸收光譜分析來決定多核鐵離子的氧化態和自旋態，也能進一步地去了解作為架橋配基的氧原子應為hydroxide (OH-)或是oxide (O2-)。 | zh_TW |
| dc.description.abstract | Abstract
Metal cluster assembly with high nuclearty and appropriate topology could sometimes have a large total spin values (S) at ground state that can function as a single-molecule magnet (SMM). The present research is focusing on the design and synthesis of polynuclear iron clusters with primarily oxygen, triazole ligands as bridging ligands. Three novel cluster compounds [Fe4(μ4-O)(μ-CH3CH2O)4(μ-dmatrz)3(NCS)6] (1), [Fe4(μ4-O)(μ-CH3O)4(μ-dmatrz)3(NCS)6] (2) and [Fe3(μ-dmatrz)4(O)(OH)(NCS)6].2H2O (3) have been synthesized and structure characterized. Complex 1 and 2 are isostructure with the cluster consists of Fe4O unit and an O atom connects to four iron atoms to form a trigonal pyramid with the average Fe-Oavg (oxo) =2.019(2) and 2.017(2); Fe-Navg(μ-dmatrz)= 2.185(4) and 2.194(4) Å for 1 and 2, respectively. Complex 3 consists of linear trinuclear iron cluster. The central iron of the cluster is located at a crystallographic inversion center and connected to two terminal iron atoms through N1,N2-bridging mode of four triazole ligands and two oxygen bridging to adopt a distorted octahedral conformation (Fe-Navg(μ-dmatrz) = 2.155 (3) and Fe-O = 1.896 (2) Å). In addition to the bridging ligands, the six-coordinated environment of the terminal iron is completed by nitrogen atoms of three NCS- anions in a fac configuration. The magnetic properties, studied by SQUID magnetometer, reveal strong antiferromagnetic interaction between the iron centers of complex 1, 2 and 3. The Fe K- and L-edge X-ray absorption spectroscopy (XAS), EPR and CV measurements are resolved the oxidation and spin state of the iron, as well as to determine the bridging oxygen atom being hydroxide or oxide. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-12T18:22:01Z (GMT). No. of bitstreams: 1 ntu-96-R94223020-1.pdf: 11737884 bytes, checksum: 0112024da193179aec50d46daed13958 (MD5) Previous issue date: 2007 | en |
| dc.description.tableofcontents | 目錄 頁碼
中文摘要 I 英文摘要 III 第一章 緒論 1 1-1 前言 1 1-2 配位基簡介 9 1-3 研究方向及成果 12 第二章 實驗部分 13 2-1 試藥與儀器 13 2-2 磁性描述與原理 16 2-3. X光吸收光譜分析 21 2-4 電化學分析 25 2-5 電子順磁共振 29 第三章 結果與討論 32 3-1 實驗合成方法 35 3-2 晶體數據之收集與處理 37 3-3 結構解析 40 3-3.1 [Fe4(μ4-O)(μ-OR)4(μ-dmatrz)3(NCS)6] ,(μ-OR= CH3CH2O(1); CH3O(2))之結構解析 40 3-3.2 [Fe3(μ-dmatrz)4(O)(OH)(NCS)6].2H2O (3)之結構解析 47 3-4. X光吸收光譜分析 52 3-4.1 Fe之K-edge 吸收光譜結果 52 3-4.2 Fe之L-edge 吸收光譜結果 58 3-5 電化學分析結果 63 3-6 電子順磁共振光譜結果 67 3-7 磁性量測與分析 69 3-7.1 [Fe4(μ4-O)(μ-OR)4(μ-dmatrz)3(NCS)6] , (μ-OR=CH3CH2O(1); CH3O(2))之磁性結果 70 3-7.2 [Fe3(dmatrz)4(O)(OH)(NCS)6].2H2O(3)之結果 71 第四章 總結 76 參考文獻 78 附錄 86 | |
| dc.language.iso | zh-TW | |
| dc.subject | 多核鐵簇 | zh_TW |
| dc.subject | X光吸收光譜 | zh_TW |
| dc.subject | 磁性 | zh_TW |
| dc.subject | polynuclear iron clusters | en |
| dc.subject | magnetic property | en |
| dc.subject | XAS | en |
| dc.title | 偶氮三唑為橋基之多核鐵簇錯合物合成.結構與磁性研究 | zh_TW |
| dc.title | Synthesis, Structure and Magnetic Characterization of dmatrz (3,5-dimethyl-4-amino-1,2,4-triazole)-base polynuclear iron complexes | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 95-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 彭旭明(Shie-Ming Peng),王志傑(Chih-Chieh Wang) | |
| dc.subject.keyword | 多核鐵簇,磁性,X光吸收光譜, | zh_TW |
| dc.subject.keyword | polynuclear iron clusters,magnetic property,XAS, | en |
| dc.relation.page | 85 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2007-08-21 | |
| dc.contributor.author-college | 理學院 | zh_TW |
| dc.contributor.author-dept | 化學研究所 | zh_TW |
| Appears in Collections: | 化學系 | |
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| ntu-96-1.pdf Restricted Access | 11.46 MB | Adobe PDF |
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