請用此 Handle URI 來引用此文件:
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/54380
完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 彭旭明(Shie-Ming Peng) | |
dc.contributor.author | Yu-Cheng Su | en |
dc.contributor.author | 蘇昱誠 | zh_TW |
dc.date.accessioned | 2021-06-16T02:53:36Z | - |
dc.date.available | 2025-12-31 | |
dc.date.copyright | 2015-07-20 | |
dc.date.issued | 2015 | |
dc.date.submitted | 2015-07-13 | |
dc.identifier.citation | [1] K. Krogmann, Angew. Chem. Internat. Edit. 1 Vol. 8 (1969) 1 No. I
[2] Kent R. Mann, Michael J. DiPierro, Thomas P. Gill, J. Am. Chem. Soc., May 21, 1980 [3] (a) Kent R. Mann and Harry B. Gray, American Chemical Society, chapter 19, pp 225–235 (b) Kent R. Mann, Nathan S. Lewis, Roger M. Williams, Harry B. Gray, and J. G. Gordoni1, Inorganic Chemistry, vol. 17, no. 4, 1978 829 (c) Kent R. Mann, Robert A. Bell, and Harry B. Gray, Inorganic Chemistry, vol. 18, no. 10, 1979 2671 (d) Kent R. Mann, John A. Thich, Robert A. Bell, Catherinel. Coyle, and Harry B. Gray, Inorganic Chemistry, vol. 19, no. 8, 1980 2463 [4] (a) L. Steven Hollis and Stephen J. Lippard, J. Am. Chem. Soc., Vol. 103, No. 5, 1981 1231 (b) Jacqueline K. Barton, David J. Szalda, Harold N. Rabinowitz, Joseph V. Waszczak,lb and Stephen J. Lippard, J. Am. Chem. Soc., March 14, 1979 [5] (a) Cristina Tejel, B. Eva Villarroya, Miguel A. Ciriano, Andrew J. Edwards, Fernando J. Lahoz, Luis A. Oro, Maurizio Lanfranchi, Antonio Tiripicchio, and Marisa Tiripicchio-Camellini, Inorg. Chem. 1998, 37, 3954-3963 (b) Cristina Tejel, Miguel A. Ciriano, B. Eva Villarroya, Raquel Gelpi, Jose A. Lo pez, Fernando J. Lahoz, and Luis A. Oro, Angew. Chem. Int. Ed. 2001, 40, No. 21 [6] Tetsuro Murahashi, Eiko Mochizuki, Yasushi Kai, and Hideo Kurosawa, J. Am. Chem. Soc. 1999, 121, 10660-10661 [7] (a) Eri Goto, Rowshan A. Begum, Shuzhong Zhan, Tomoaki Tanase,* Katsumi Tanigaki, and Ken Sakai, Angew. Chem. Int. Ed. 2004, 43, 5029 –5032 (b) Yukie Takemura, Hiroe Takenaka, Takayuki Nakajima, and Tomoaki Tanase, Angew. Chem. Int. Ed. 2009, 48, 2157 –2161 [8] John F. Berry, F. Albert Cotton, Peng Lei, Tongbu Lu, and Carlos A. Murillo, Inorganic Chemistry, Vol. 42, No. 11, 2003 [9] M. Be´nard, J. F. Berry, F. A. Cotton, C. Gaudin, X. Lo´pez, C. A. Murillo, and M.-M. Rohmer, Inorganic Chemistry, Vol. 45, No. 10, 2006 [10] 林子偉,國立台灣大學化學研究所碩士論文 [11] Chih-Hsien Chien, Jung-Che Chang, Chen-Yu Yeh, Gene-Hsiang Lee, Jim-Min Fang and Shie-Ming Peng, Dalton Trans., 2006, 2106–2113 [12] Ming-Chuan Cheng, Isiah Po-Chun Liu, Chan-Hsiang Hsu, Gene-Hsiang Lee, Chun-hsien Chen and Shie-Ming Peng, Dalton Trans., 2012, 41, 3166–3173 [13] Isiah Po-Chun Liu, Wen-Zhen Wang and Shie-Ming Peng, Chem. Commun., 2009, 4323–4331 [14] Rayyat H. Ismayilov, Wen-Zhen Wang, Gene-Hsiang Lee, Chen-Yu Yeh, Shao-An Hua, You Song, Marie-Madeleine Rohmer, Marc B e´nard, and Shie-Ming Peng, Angew. Chem. Int. Ed. 2011, 50, 2045 –2048 [15] (a) Chih-Hsien Chien, Jung-Che Chang, Chen-Yu Yeh, Gene-Hsiang Lee, Jim-Min Fang, You Song and Shie-Ming Peng, Dalton Trans., 2006, 3249–3256 (b) Chih-Hsien Chien, Jung-Che Chang, Chen-Yu Yeh, Gene-Hsiang Lee, Jim-Min Fang and Shie-Ming Peng, Dalton Trans., 2006, 2106–2113 [16] Shao-An Hua, Isiah Po-Chun Liu, Hasan Hasanov, Gin-Chen Huang, Rayyat Huseyn Ismayilov, Chien-Lan Chiu, Chen-Yu Yeh, Gene-Hsiang Lee and Shie-Ming Peng, Dalton Trans., 2010, 3890–3896 [17] Jau-Huei Kuo, Ting-Bin Tsao, Gene-Hsiang Lee, Hsuan-Wei Lee, Chen-Yu Yeh, and Shie-Ming Peng, Eur. J. Inorg. Chem. 2011, 2025–2028 [18] Che-Wei Yeh, Isiah Po-Chun Liu, Rui-Ren Wang, Chen-Yu Yeh, Gene-Hsiang Lee, and Shie-Ming Peng, Eur. J. Inorg. Chem. 2010, 3153–3159 [19] Cherng-Shiaw Tsai, Isiah Po-Chun Liu, Fang-Wei Tien, Gene-Hsiang Lee, Chen-Yu Yeh, Chun-hsien Chen, Shie-Ming Peng, Inorganic Chemistry Communications 2013, 152–155 [20] 羅鈺霖,國立台灣大學化學研究所碩士論文 [21] Shao-An Hua, Gin-Chen Huang, Isiah Po-Chun Liu, Jau-Huei Kuo, Ching-Hong Jiang, Chien-Lan Chiu, Chen-Yu Yeh, Gene-Hsiang Lee and Shie-Ming Peng, Chem. Commun., 2010, 5018–5020 [22] Wen-Zhen Wang, Yang Wu, Rayyat H. Ismayilov, Juao-Hui Kuo, Chen-Yu Yeh, Hsuan-Wei Lee, Ming-Dung Fu, Chun-hsien Chen, Gene-Hsiang Lee and Shie-Ming Peng, Dalton Trans., 2014, 6229–6235 [23] Wen-Zhen Wang, Rayyat Huseyn Ismayilov, Gene-Hsiang Lee, Isiah Po-Chun Liu, Chen-Yu Yeh and Shie-Ming Peng, Dalton Trans., 2007, 830–839 [24] (a) D. Gatteschi, C. Mealli, L. Sacconi, J. Am. Chem. Soc. 1973, 95, 2736. (b) L. Sacconi, C. Mealli, D. Gatteschi. Inorg. Chem., 1974, 13, 1985.16. (c) A. Bencini, E. Berti, A. Caneschi, D. Gatteschi, E. Giannasi and I. Invernizzi, Chem. Eur. J., 2002, 3660. [25] (a) Anders Dossing, Sine Larsen, Alexander van Lelieveld and Rikke Mattsson Bruun, Acta Chemica Scandinavica, 1999, 53, 230 – 234 (b) Rodolphe Cle´rac, F. Albert Cotton, Lee M. Daniels, James P. Donahue, Carlos A. Murillo, and Daren J. Timmons, Inorg. Chem., 2000, 39, 2581-2584 [26] T. J. Hurley, M. A. Robinson, Inorg. Chem. 1968, 7, 33. [27] L. P. Wu, P. Field, T. Morrissey, C. Murphy, P. Nogle and B. Hathaway, J. Chem. Soc. Dalton Trans., 1990,3835. [28] Pyrka, G. J.; El-Mekki, M.;Pinkerton, A. A. J. Chem.Soc., Chem. Commun., 1991, 84 [29] S. Aduldecha and B. Hathaway, J. Chem. Soc. Dalton Trans., 1991, 993 [30] (a) Michael Nippe, Eric Victor, and John F. Berry, Inorg. Chem., 2009, 48, 11889–11895 (b) Michael Nippe, Eckhard Bill, and John F. Berry, Inorg. Chem., 2011, 50, 7650–7661 (c) Michael Nippe and John F. Berry, J. AM. CHEM. SOC., 2007, 129, 12684-12685 [31] Jinn-Tsair Sheu, Cheng-Chen Lin, Ito Chao, Chih-Chieh Wang and Shie-Ming Peng, Chem. Commun., 1996 315 [32] (a) Gin-Chen Huang, Marc Bénard, Marie-Madeleine Rohmer, Long-An Li, Mei-Jyun Chiu, Chen-Yu Yeh, Gene-Hsiang Lee, and Shie-Ming Peng, Eur. J. Inorg. Chem., 2008, 1767–1777 (b) Isiah Po-Chun Liu, Gene-Hsiang Lee, Shie-Ming Peng, Marc Be´nard, and Marie-Madeleine Rohmer, Inorg. Chem., 2007, 46, 9602-9608 [33] Ming-Chuan Cheng, Chi-Lun Mai, Chen-Yu Yeh, Gene-Hsiang Lee and Shie-Ming Peng, Chem. Commun., 2013, 49, 7938 [34] 江意利,國立台灣大學化學研究所博士論文 [35] Rayyat H. Ismayilov, Wen-Zhen Wang, Rui-Ren Wang, Chen-Yu Yeh, Gene-Hsiang Lee and Shie-Ming Peng, Chem. Commun., 2007, 1121–1123 [36] Gin-Chen Huang, Shao-An Hua, Isiah Po-Chun Liu, Chih-Hsien Chien, Jau-Huei Kuo, Gene-Hsiang Lee, Shie-Ming Peng, C. R. Chimie, 15 2012 159–162 [37] 王瑞仁,國立台灣大學化學研究所博士論文 [38] Hasanov Hasan, Uan-Kang Tan, Gene-Hsiang Lee, Shie-Ming Peng, Inorganic Chemistry Communications, 10 2007 983–988 [39] J. P. Wibaut; E. Dingemasse, Rec.Trav.Chim.Pays-Bas, 1923,42,243 [40] S. Wagan and S. L. Buchwald, J. Org. Chem., 1996,61,7240. [41] Charles O. Okafor, J. Heterocyclic Chem., 1976, 13, 107–110. [42] Ferrarini, P. L., Mori, C., Badawneh, M., Manera, C., Martinelli, A., Romagnoli, F., Saccomanni, G. and Miceli, M, J. Heterocyclic Chem., 1997, 34, 1501–1510 [43] M. Wozniak, W. Roszkiewicz, Synthesis, 1976; 1976 691-692 | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/54380 | - |
dc.description.abstract | 對於合成更長鏈的金屬串錯合物,多吡啶胺配基會以syn或anti方式來與金屬作配位,影響著金屬串錯合物的產率高低和副產物多寡,設計將配基只能以syn配位方式來反應,用來解決在多核金屬串錯合物會發生的低產率和多副產物之現象。本論文研究目的為合成不對稱剛性四氮配基(Htzbp)及其金屬串錯合物,並與本實驗室王瑞仁學長合成出一系列四氮配基(Hpyany, Hpzany, Hpcany)及其金屬串錯合物做比較和討論。
將Hpyany的萘啶環和吡啶環以氧鍵結,形成一剛性的新型配基。透過硝化反應、氯化反應及cross coupling,合成出Htzbp (1,2,11-triazabenzo[b]phenoxazine)。將此單晶結構與其他不對稱四氮配基單晶做比較。 利用本實驗室獨特的萘燒法,在高溫220 oC下與金屬反應,形成一含四片配基且直線型金屬串錯合物。不對稱配基合成出的金屬串可能具有四種形式,分別為(4,0)、(3,1)、(2,2-cis)及(2,2-trans),將配基修飾一立體障礙較大的官能基,可控制其金屬串錯合物為(4,0)的配位形式。而Htzbp不具有立體障礙的官能基,因此可能具有四種形式的金屬串錯合物。 [Ni4(tzbp)4(NCS)2](NCS) (2)的X-ray單晶繞射分析,四個配基雖然有失序的情況,但Ni(1)-Ni(2) = 2.4063(9) Å、Ni(2)-Ni(3) = 2.4078(9) Å、Ni(3)-Ni(4) = 2.4300(9) Å,為一個不對稱的鍵長長度;藉由電化學可以發現僅有一組可逆氧化還原電位的訊號;磁性分析上,萘啶單元[Ni2]3+電子組態為S = 3/2,Ni(4)為為獨立之高自旋d8電子組態S = 1;可推斷其為(4,0)[Ni4(tzbp)4(NCS)2](NCS)四核鎳金屬串錯合物。 | zh_TW |
dc.description.abstract | In order to avoid the potential problem of several side products for synthesizing longer metal strings, the syn mode plays a crucial role. Our lab had been successfully synthesized Hdzp ligand (1,9-diazaphenoxazine), which limited the syn coordination mode of oligo-α-pyridylamine ligands by binding their pyridine rings. Here we present the design and preparation of new unsymmetrical tetra-dentate ligand, Htzbp (1,2,11-triazabenzo[b]phenoxazine), which is rigid by binding 1,8-napthyridine and pyridine ring, and the studies of their tetra-nickel string complexes.
A new ligand, 1,2,11-triazabenzo[b]phenoxazine (Htzbp), is synthesized by nitrification, chlorination and the cross-coupling of 2-chloro-3-nitro-1,8-naphthyridine with 2-amnio-3-hydroxypyridine. The single crystal of Htzbp is studied. The linear tetra-nickel string complexes are synthesized through reacting of ligand with Ni(OAc)2•4H2O. Because of the unsymmetrical ligand , there are four possible geometrical isomers of the tetra-nickel string complexes from the orientations of the ligands, abbreviated as (4,0), (3,1), (2,2-cis) and (2,2-trans) forms. Lack of the steric hindrance of the bulky functional group, [Ni4(tzbp)4(NCS)2](NCS) (2) could be one of four geometric isomers. From the experimental results of X-ray crystallography, the four sets of ligand have the disorder situation, we find out that Ni(1)-Ni(2) = 2.4063(9) Å, Ni(2)-Ni(3) = 2.4078(9) Å and Ni(3)-Ni(4) = 2.4300(9) Å are unsymmetrical Ni-Ni bond length. The electrochemical study shows that there is only one set reversible signal, E1/2(oxi) = +0.2683 V and E1/2(red) = -0.1720 V. The magnetism of linear tetra-nickel string complex is studied, after one electron reduction that occurred in the two nickel atoms at the position of naphthyridine rings, the spin state of the two nickel atom is S = 3/2. As the results of those, we suggest that (4,0)[Ni4(tzbp)4(NCS)2](NCS) is obtained. | en |
dc.description.provenance | Made available in DSpace on 2021-06-16T02:53:36Z (GMT). No. of bitstreams: 1 ntu-104-R02223168-1.pdf: 7345986 bytes, checksum: f6f57fe3cb2201557559d4b34dd16c47 (MD5) Previous issue date: 2015 | en |
dc.description.tableofcontents | 口試委員會審定書
中文摘要 I 英文摘要 II 第一章 緒論 1 1-1 分子金屬導線 1 1-2 金屬-金屬鍵結理論 5 1-2-1 雙核金屬錯合物 5 1-2-2 三核金屬錯合物 7 1-2-3 四核金屬錯合物 9 1-2-4 六核金屬錯合物 11 1-3 多氮配基簡介 12 1-3-1 多吡啶胺配基 12 1-3-2 多萘啶胺配基 14 1-3-3 吡啶萘啶胺混合配基 14 1-3-4 吡啶胺或萘啶胺之衍生或微調配基萘啶衍生配基金屬錯合物 17 1-4 萘啶衍生配基金屬錯合物 17 1-5 直線型多核金屬串錯合物 19 1-5-1 奇數核直線型金屬串錯合物 21 1-5-2 四核及其他偶數核直線型金屬串錯合物 24 1-6 研究方向 28 第二章 實驗部分 29 2-1 試藥與儀器 29 2-1-1 試藥 29 2-1-2 儀器 31 2-2 配基合成 32 2-3 四核鎳金屬串錯合物合成 37 第三章 萘啶吡啶胺之合成與性質 39 3-1 不對稱萘啶吡啶胺配基 39 3-1-1 配基設計與合成 40 3-1-2 不對稱萘啶吡啶胺配基支配位模式 42 3-1-3 不對稱萘啶吡啶胺配基所合成的金屬串錯合物 44 3-2 結構分析與討論 45 第四章 四核鎳金屬串錯合物 48 4-1 合成 48 4-2 晶體結構分析與討論 48 4-3 磁性量測與分析 53 4-4 電化學分析 59 4-4-1 不對稱四氮配基 59 4-4-2 直線型四核鎳金屬串錯合物 60 4-5 電子吸收光譜 63 4-5-1 不對稱四氮配基 64 4-5-2 不對稱四氮配基(Htzbp)及其四核鎳金屬串錯合物 65 第五章 總結 66 參考文獻 67 附錄 71 NMR光譜 72 ESI - MS & MALDI - MS質譜 75 IR光譜 79 晶體結構及晶體數據 81 | |
dc.language.iso | zh-TW | |
dc.title | 萘啶吡啶胺剛性配基及其直線型四核鎳金屬串錯合物之合成與研究 | zh_TW |
dc.title | Syntheses and Studies of Linear Tetra-Nickel Metal String Complexes with the New Rigid Ligand | en |
dc.type | Thesis | |
dc.date.schoolyear | 103-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 王志傑,金必耀,陳俊顯 | |
dc.subject.keyword | 四核鎳金屬串錯合物,剛性配基,不對稱型配基,三氮苯吩,偶數核金屬串錯合物, | zh_TW |
dc.subject.keyword | tetra-nickel metal string complexes,rigid ligand,unsymmetrical ligand,1,2,11-triazabenzo[b]phenoxazine,even-numbered metal string complexes, | en |
dc.relation.page | 89 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2015-07-13 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 化學研究所 | zh_TW |
顯示於系所單位: | 化學系 |
文件中的檔案:
檔案 | 大小 | 格式 | |
---|---|---|---|
ntu-104-1.pdf 目前未授權公開取用 | 7.17 MB | Adobe PDF |
系統中的文件,除了特別指名其著作權條款之外,均受到著作權保護,並且保留所有的權利。