跳到主要內容

臺灣博碩士論文加值系統

(18.97.14.86) 您好!臺灣時間:2025/02/09 00:24
字體大小: 字級放大   字級縮小   預設字形  
回查詢結果 :::

詳目顯示

: 
twitterline
研究生:吳明霈
研究生(外文):Ming-Pei Wu
論文名稱:二胺基二醯胺金屬錯合物色變材料之研究
論文名稱(外文):Study on Chromic Materials of Transition Metal Diaminodiamide Complexes
指導教授:趙敏勳
指導教授(外文):Min-Shiun Chao
學位類別:碩士
校院名稱:國立勤益科技大學
系所名稱:化工與材料工程系
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:中文
論文頁數:173
中文關鍵詞:錯合物超分子轉換二胺基二醯胺
外文關鍵詞:ComplexSupramolecularSwitchingDiaminodiamide
相關次數:
  • 被引用被引用:0
  • 點閱點閱:188
  • 評分評分:
  • 下載下載:6
  • 收藏至我的研究室書目清單書目收藏:0
近年來,以第一列過渡金屬作為配位中心是個熱門的選擇,用來設計和探討材料的配位行為。一個廣泛的金屬中心藉由多功能有機配位基連結形成配位聚合物(coordination polymers, CPs)和金屬有機骨架(metal-organic frameworks, MOFs),這些性質用於設計新的3D網絡,應用於離子交換、催化及分離上。本論文以Michael Addition方式設計合成三種含有二胺基二醯胺配位基(diaminodiamide ligand),分別為4,7-Diazadecanediamide (L-2,2,2)、4-methyl-4,7-diazadecanediamide
(4-Me-L-2,2,2)及4,7-Dimethyl-4,7-diazadecanediamide (4,7-Me2-L-2,2,2)。利用此三種配位基與過渡金屬(Cr3+, Ni2+, Cu2+)配位進行自組裝反應,藉由分子間氫鍵作用力形成具有特殊架構之超分子。
利用半活性配位子L-2,2,2與過渡金屬(Ni2+)配位形成前驅物再加入亞硝酸根(NO2-)為合成策略製備出藍色的[Ni(C8H18N4O2)(NO2)2] • H2O (1) ,以NaOH調控pH值在鹼性溶液中重組形成黃色四配位[Ni(C8H16N4O2)]‧3H2O (2)。使用半活性配位子4,7-Me2-L-2,2,2與過渡金屬離子(Cu2+)配位形成藍紫色五配位[Cu(C10H22N4O2)(Cl)](Cl) (3), 以NaOH調控pH值在鹼性溶液中重組形成紫色的四配位的[Cu(C8H16N4O2) ] ‧2H2O (4), 繼續放置在鹼性環境下, 胺基會水解成羧酸根形成藍色的配位聚合物[Cu(C10H18N2O4) ‧3H2O]n (5)。利用半活性配位子L-2,2,2與不同過渡金屬陽離子(Cr3+, Ni2+, Cu2+)配位形成紫色鹽類[C8H20N4O2]‧Cl2 (6)、淺藍色六配位[Ni(C8H18N4O2)(H2O)2]‧2Cl (7)及藍色五配位[Cu(C8H18N4O2)(Cl)]Cl‧2H2O (8),分別探討反應機制與結構性質。以4-Me-L-2,2,2與過渡金屬(Cu2+)形成藍色六配位[Cu(C9H20N4O2)(SO4)(H2O)]•2H2O (9),研究不同結構的配位基與(Cu2+)產生不同的配位模式和結構,探討立體效應對錯合物結構的影響。
所得產物則藉由元素分析( EA )、傅立葉紅外線光譜儀(FT-IR)及X-ray 單晶繞射確定晶體結構並探討解析其在空間上之排列組裝架構,材料的熱穩定性則藉由熱重分析儀(TGA)來探討,紫外/可見光光譜(uv/vis)證明其配位基與金屬,形成錯合物的吸收光譜。

Recently, first row transition metals are popular choice as the coordination centers for the design and discovery of these materials coordination behavior. A wide range of metal-center coordination polymers (CPs) and frameworks (MOFs) through linkages with multifunctional organic ligands. These properties are used to design three-dimensional (3-D) networks useful in ion exchange, catalysis, and separation. In this thesis, we use Michael addition reaction to design and synthesize three kind of diaminodiamide ligands that are 4,7-Diazadecanediamide(L-2,2,2), 4-methyl-4,7-diazadecanediamide (4-Me-L-2,2,2), 4,7-Dimethyl-4,7-diazadecanediamide (4,7-Me2-L-2,2,2), respectively. We utilize these ligands with transition metal ions (Cr3+, Cu2+, Ni2+) to proceed self-assembly reaction, and through intermolecular hydrogen-bonding interactions to generate special supramolecular architecture.
we used flexible hemilabile L-2,2,2 ligand with transition metal ion (Ni2+) to form a precursor via coordination, then added into nitrite(NO2-) to yield [Ni(C8H18N4O2)(NO2)2] • H2O (1), and this compound was reorganized in basic solution, resulting in [Ni(C8H16N4O2)]‧3H2O (2). Then we utilize flexible hemilabile 4,7-Me2-L-2,2,2 ligand with transition metal ion (Cu2+) to yield five-coordinated [Cu(C10H22N4O2)(Cl)](Cl) (3), and the compound was reorganized in basic solution, resulting in four-coordinated [Cu(C8H16N4O2) ] ‧2H2O (4), when the compound stayed in basic solution over one month, the amido groups were hydrolyzed to form five-coordinated polymer [Cu(C10H18N2O4) ‧3H2O]n (5) with carboxyl groups.
In the end, we utilize different transition metal ions (Cr3+, Ni2+, Cu2+) with flexible hemilabile L-2,2,2 ligand to yield salt [C8H20N4O2]‧Cl2 (6), six-coordinated [Ni(C8H18N4O2)(H2O)2]‧2Cl (7) and five-coordinated [Cu(C8H18N4O2)(Cl)]Cl‧2H2O (8), respectively, and then study these compounds’ reaction mechanism, structure and physical property. In order to study steric effect of complex structure, we used different flexible hemilabile 4-Me-L-2,2,2 ligand with transition metal ion (Cu2+) to yield six-coordinated [Cu(C9H20N4O2)(SO4)(H2O)]•2H2O (9).
These compounds were structurally characterized by elemental analyzer, Fourier Transform infrared spectrometer and single-crystal X-ray diffraction method, and their thermal stabilities were studied by thermogravimetric analyzer. Electronic spectra behaviors were studied by UV/Vis spectrophotometer .

中文摘要 ii
英文摘要 iv
誌謝 vi
目錄 viii
表目錄 xi
圖目錄 xiii
第一章 緒論 1
1.1前言 1
1.2 超分子化學之起源與定義 3
1.3分子開關 8
1.4 分子開關合成條件 10
1.5 配位聚合物 12
第二章 實驗設備、方法與程序 14
2.1藥品 14
2.2儀器 15
2.3 合成 17
第三章 結果與討論 27
3.1 配位子 L-2,2,2的製備 28

3.2-1[Ni(C8H18N4O2)(NO2)2] • H2O (1) 的合成、鑑定及自
組裝 29
3.2-2 化合物1在水溶液的重組 34
3.2-3 [Ni(C8H16N4O2)]‧3H2O (2)的合成、鑑定及自組
裝 35
3.2-4光物理性質 40
3.3配位子4,7-Me2-L-2,2,2的製備 43
3.4-1 [Cu(C10H22N4O2)(Cl)](Cl) (3)的合成、鑑定及自組
裝 44
3.4-2 熱穩定分析 49
3.4-3 化合物3在水溶液的重組 50
3.4-4 [Cu(C10H18N2O4) ‧3H2O]n (5)的合成、鑑定及自組
裝 51
3.4-5 熱穩定分析 57
3.4-6 光物理性質 58
3.5-1 [C8H20N4O2]‧Cl2 (6)的合成、鑑定及自組裝 61
3.6-1 [Ni(C8H18N4O2)(H2O)2]‧2Cl (7)的合成、鑑定及自組
裝 67
3.7-1 [Cu(C8H18N4O2)(Cl)]Cl‧2H2O (8)的合成、鑑定及自組
裝 73
3.8配位子4-Me-L-2,2,2的製備 77
3.9-1[Cu(C9H20N4O2)(SO4)(H2O)]•2H2O (9)的合成、鑑定
及自組裝 78
3.10化合物6、化合物7及化合物8的過渡金屬性質探討 84
3.11化合物3及化合物9的立體效應探討 88
結論 93
參考文獻 95
附錄 100

1. H. D. Guo,; X. M. Guo,; S. R. Batten,; J. F. Song,; S. Y. Song,; S. Dang,;
G. L. Zhang,; J. K. Tang,; H. J. Zhang, Crystal Growth &; Design., 2009, 9, 1394–1401.
2. Y. Wei,; H. Hou,; L. Li,; Y. Fan,; Y. Zhu,; S. Dang , Crystal Growth &; Design., 2005, 5, 1405–1413.
3. X. Wang,; C. Qin,; E. Wang,; Y. Li,; N. Hao,; C. Hu,; L. Xu, Inorg. Chem., 2004, 43, 1850–1856.
4. J. Hunger,; H. Krautscheid,; J. Sieler, Crystal Growth &; Design., 2009, 9 , 4613–4625.
5. J. M. Lehn, Chem. Soc. Rev., 2007, 36, 151–160.
6. J.-M. Lehn, Proc. Natl. Acad. Sci. U. S. A., 2002, 99, 4763.
7. J.-M. Lehn, Science, 2002, 295, 2400.
8. D. Gust,; T. A. Moore,; A. L. Moore, Acc. Chem. Res. 2001, 34, 40.
9. G. W. Gokel,; A. Mukhopadhyav, Chem. Soc. Rev. 2001, 30, 274.
10. D. T. Bong,; T. D. Clark,; J. R. Granja,; M. R. Ghadiri, Angew. Chem., Int. Ed. 2001, 40, 988.
11. M. Irie, Chem. Rev. 2000, 100, 1683.
12. A. P. de Silva,; N. D. McClenaghan, J. Am. Chem. Soc. 2000, 122, 3965.
13. M. S. Masar III,; N. C. Gianneschi,; C. G. Oliveri,; C. L. Stern,; S. T. Nguyen,; C. A. Mirkin, J. Am. Chem. Soc. 2007, 129, 10149.
14. N. C. Gianneschi,; P. A. Bertin,; S. T. Nguyen,; C. A. Mirkin,; L. N. Zakharov,; A. L. Rheingold, J. Am. Chem. Soc. 2003, 125, 10508.
15. N. C. Gianneschi,; S.-H. Cho,; S. T. Nguyen,; C. A. Mirkin, Angew. Chem. Int. Ed. 2004, 43, 5503.
16. N. C. Gianneschi,; S. T. Nguyen,; C. A. Mirkin, J. Am. Chem. Soc. 2005, 127, 1644-1645.
17. C. G. Oliveri,; N. C. Gianneschi,; S. T. Nguyen,; C. A. Mirkin,; C.
L. Stern,; Z. Wawrzak,; M. Pink, J. Am. Chem. Soc. 2006, 128, 16286.
18. L. Han,; Y. Gong,; D. Yuan,; M. Hong, Journal of molecular structure, 2006, 789, 128–132
19. J. R. Nitschke,; J.-M. Lehn, Proc. Natl. Acad. Sci. U. S. A., 2003, 100, 11970.
20. J.-M. Lehn, Angew. Chem., Int. Ed. Engl. 1990, 29, 1304.
21. J.-M. Lehn, Chem.–Eur. J. 2000, 6, 2097.
22. B. Hasenknopf,; J.-M. Lehn,; B. O. Kneisel,; G. Baumand,; D. Fenske, Angew. Chem., Int. Ed. Engl., 1996, 35, 1838;
23. B. Hasenknopf,; J.-M. Lehn,; N. Boumediene,; A. Dupont-Gervais,; A. Van Dorsselaer,; B. Kneisel.; D. Fenske, J. Am. Chem. Soc. 1997, 119, 10956.
24. J.-M. Lehn, Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 4763.
25. J.-M. Lehn, Science, 2002, 295, 2400.
26. J.-M. Lehn, Prog. Polym. Sci., 2005, 30, 814.
27. J.-M. Lehn, Chem.–Eur. J. 1999, 5, 2455.
28. O. Ramstro¨m,; J.-M. Lehn, Nat. Rev. Drug Discovery, 2002, 1, 26.
29. S. J. Rowan,; S. J. Cantri l l,; G. R. L. Cousins,; J. K. M. Sanders,; J. F. Stoddart, Angew. Chem., Int. Ed. 2002, 41, 898.
30. J. D. Cheeseman,; A. D. Corbett,; J. L. Gleason,; R. J. Kazlauskas, Chem.–Eur. J. 2005, 11, 1708.
31. P. T. Corbett,; J. Leclaire,; L. Vial,; K. R. West,; J.-L. Wietor,; J. K. M. Sanders,; S. Otto, Chem. Rev. 2006, 106, 3652.
32. M. Kruppa,; B. Ko¨ nig, Chem. Rev. 2006, 106, 3520.
33. M. Crego Calama,; R. Hulst,; R. Fokkens,; N. M. M. Nibbering,; P. Timmerman,; D. N. Reinhoudt, Chem. Commun. 1998, 1021.
34. P. Timmerman,; R. H. Vreekamp,; R. Hulst,;W. Verboom,; D. N. Reinhoudt,; K. Rissanen,; K. A. Udachin,; J. Ripmeester, Chem.–Eur. J. 1997, 3, 1823.
35. M.M. Cai,; X. D. Shi,; V. Sidorov,; D. Fabris,; Y. F. Lam,; J. T. Davis, Tetrahedron, 2002, 58, 661
36. A. Gasnier,; J. –M. Barbe,; C. Bucher,; F. Denat,; J. –C. Moutet,;
E. Saint-Aman,; P. Terech,; G. Royal, Inorg. Chem. 2008, 47, 1862.
37. K. Harano,; S. Hiraoka,; M. Shionoya, J. Am. Chem. Soc. 2007, 129,
5300.
38. J. -M. Lehn, Chem. Soc. Rev. 2007, 36, 151.
39. T. Yamamoto,; A. M. Arif,; P. J. Stang, J. Am. Chem. Soc. 2003, 125, 12309.
40. S. -S. Sun,; C. L. Stern,; S. -B. T. Nguyen,; J. T. Hupp, J. Am. Chem. Soc. 2004, 126, 6314.
41. A. M. Brown,; M. V. Ovchinnikov,; C. L. Stern,; C. A. Mirkin, J. Am. Chem. Soc. 2004, 126, 14316.
42. S. Hivaoka,; K. Harano,; M. Shiro,; M. Shionoya, Angew. Chem., Int. Ed. 2005, 4, 2727.
43. K. Harono,; S. Hiraoka,; M. Shionoya, J. Am. Chem. Soc. 2007, 129, 5300.
44. D. Kalny,; M. Elhabiri,; T. Moab,; A. Vaskevich,; I. Rudinstein,; A. Shanzer,; A. -M. Albracht-Gary, Chem. Commun. 2002, 1426.
45. R. A. Bissel,; E. Lvdova,; A. E. Kaifer,; J. F. Stoddart, Nature 1994, 369, 133.
46. S. Shinkai,; M. Ikoda, A. Sugasaki, M. Takeuchi, Acc. Chem. Res.
2001,34, 494.
47. L. Feringa, Acc. Chem. Res. 2001, 34, 504.
48. V. A. Soloshonok,; H. Ueki,; J. L. Moore,; T. K. Ellis, J. Am. Chem. Soc. 2007, 129, 3512.
49. M. S. Chao,; H. H. Lu,; M. L. Tsai,; M. C. Ho,; T. H. Hsieh, Inorg. Chem. Commun. 2008, 11, 1445.
50. D. Banerjee,; S. J. Kim,; L. A. Borkwski,; W. Xu, Crystal Growth &; Design., 2010, 10, 709–715.
51. . H. C. Wu,; P. Thanasekaran,; C. H. Tsai,; J. Y. Wu,; S. M. Huang,; Y. S. Wen,; K. L. Lu, Inorg. Chem. 2006, 45, 295-303.
52. 何美蟬, 國立勤益科技大學化工與材料工程研究所碩士論文,中華
民國九十六年六月
53. 謝宗軒, 國立勤益科技大學化工與材料工程研究所碩士論文,中華
民國九十八年六月
54. 林千閔, 國立勤益科技大學化工與材料工程研究所碩士論文,中華
民國一百年六月

連結至畢業學校之論文網頁點我開啟連結
註: 此連結為研究生畢業學校所提供,不一定有電子全文可供下載,若連結有誤,請點選上方之〝勘誤回報〞功能,我們會盡快修正,謝謝!
QRCODE
 
 
 
 
 
                                                                                                                                                                                                                                                                                                                                                                                                               
第一頁 上一頁 下一頁 最後一頁 top
無相關期刊