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http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/46110完整後設資料紀錄
| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 邱勝賢(Sheng-Hsien Chiu) | |
| dc.contributor.author | Ming-Liang Yen | en |
| dc.contributor.author | 顏名良 | zh_TW |
| dc.date.accessioned | 2021-06-15T04:54:16Z | - |
| dc.date.available | 2013-07-30 | |
| dc.date.copyright | 2010-07-30 | |
| dc.date.issued | 2010 | |
| dc.date.submitted | 2010-07-29 | |
| dc.identifier.citation | 1. (a) Armaroli, N.; Balzani, V.; Collin, J.-P.; Gaviña, P.; Sauvage, J.-P.; Ventura, B. J. Am. Chem. Soc. 1999, 121, 4397–4408. (b) Altieri, A.; Gatti, F. G.; Kay, E. R.; Leigh, D. A.; Martel, D.; Paolucci, F.; Slawin, A. M. Z.; Wong, J. K. Y. J. Am. Chem. Soc. 2003, 125, 8644–8654. (c) Jeon, W. S.; Ziganshina, A. Y.; Lee, J. W.; Ko, Y. H.; Kang, J.-K.; Lee, C.; Kim, K. Angew. Chem. Int. Ed. 2003, 42, 4097–4100. (d) Tseng, H.-R.; Vignon, S. A.; Celestre, P. C.; Perkins, J.; Jeppesen, J. O.; Di Fabio, A.; Ballardini, R.; Gandolfi, M. T.; Venturi, M.; Balzani, V.; Stoddart, J. F. Chem. Eur. J. 2004, 10, 155–172.
2. (a) Ballardini, R.; Balzani, V.; Clemente-Leon M.; Credi, A.; Gandolfi, M. T.; Ishow, E.; Perkins, J.; Stoddart, J. F.; Tseng, H.-R.; Wenger, S. J. Am. Chem. Soc. 2002, 124, 12786–12795. (b) Berna, J.; Leigh, D. A.; Lubomska, M.; Mendoza, S. M.; Perez, E. M.; Rudolf, P.; Teobaldi, G.; Zerbetto, F. Nature Mater. 2005, 4, 704–710. (c) Saha, S.; Stoddart, J. F. Chem. Soc. Rev. 2007, 36, 77–92. (d) Pijper, D.; Jongejan, M. G. M.; Meetsma, A.; Feringa, B. L. J. Am. Chem. Soc. 2008, 130, 4541–4552. 3. (a) Kaiser, G.; Jarrosson, T.; Otto, S.; Ng, Y.-F.; Bond, A. D.; Sanders, J. K. M. Angew. Chem. Int. Ed. 2004, 43, 1959–1962. (b) Huang, F.; Switek, K. A.; Gibson, H. W. Chem. Commun. 2005, 3655–3657. (c) Yen, M.-L.; Li, W.-S.; Lai, C.-C.; Chao, I.; Chiu, S.-H. Org. Lett. 2006, 8, 3223–3226. (d) Huang, Y.-L.; Hung, W.-C.; Lai, C.-C.; Liu, Y.-H.; Peng, S.-M.; Chiu, S.-H. Angew. Chem. Int. Ed. 2007, 46, 6629–6633. (e) Lin, T.-C.; Lai, C.-C.; Chiu, S.-H. Org. Lett. 2009, 11, 613–616. 4. For reviews, see: (a) Balzani, V.; Credi, A.; Raymo, F. M.; Stoddart, J. F. Angew. Chem. Int. Ed. 2000, 39, 3348–3391. (b) Kay, E. R.; Leigh, D. A.; Zerbetto, F. Angew. Chem. Int. Ed. 2007, 46, 72–191. (c) Champin, B.; Mobian, P.; Sauvage, J.-P. Chem. Soc. Rev. 2007, 36, 358–366. 5. (a) Cheng, P.-N.; Chiang, P.-T.; Chiu, S.-H. Chem. Commun. 2005, 1285–1287. (b) De Silva, A. P.; Uchiyama, S. Nature Nanotech. 2007, 2, 399–410. (c) Magri, D. C.; Vance, T. P.; Silva, A. P. D. Inorg. Chim. Acta 2007, 360, 751–764. (d) Zhang, D.; Su, J.; Ma, X.; Tian, H. Tetrahedron 2008, 64, 8515–8521. 6. Lin, C.-F.; Liu, Y.-H.; Lai, C.-C.; Peng, S.-M.; Chiu, S.-H Angew. Chem. Int. Ed. 2006, 45, 3176–3181. 7. (a) Gokel, G. W.; Cram, D. J. J. Chem. Soc., Chem. Commun. 1973, 481–482. (b) Bartsch, R. A.; Chen, H.; Haddock, N. F.; Juri, P. N. J. Am. Chem. Soc. 1976, 98, 6753–6754. (c) Izatt, R. M.; Lamb, J. D.; Swain, C. S.; Christensen, J. J.; Haymore, B. L. J. Am. Chem. Soc. 1980, 102, 3032–3034. 8. We determined the association constant (Ka) for the complex formed from these two species to be 2.9 x 108 M-1, through 1H NMR spectroscopic competition experiments using 1,2-bis(methylpyridinium)ethane as the competing reagent. Using an isothermal titration calorimetry (ITC)-based competition experiment, we determined the binding constant between the molecular cage 1 and 1,2-bis(methylpyridinium)ethane in CHCl3/CH3CN (1:1) to be 1.8 x 108 M–1. For examples of the use of this method to obtain association constants for other molecular recognition systems, see: (a) Velazquez-Campoy, A.; Freire, E. Nat. Protoc. 2006, 1, 186–191. (b) Rekharsky, M. V.; Mori, T.; Yang, C.; Ko, Y. H.; Selvapalam, N.; Kim, H.; Sobransingh, D.; Kaifer, A. E.; Liu, S.; Isaacs, L.; Chen, W.; Moghaddam, S.; Gilson, M. K.; Kim, K.; Inoue, Y. Proc. Natl. Acad. Sci. USA 2007, 104, 20737–20742. 9. Crystal data for [(1 2)∙3MeCN•2PF6]: [C79H95O16N7][PF6]2, Mr = 1688.56, triclinic, space group P-1, a = 14.3156 (7), b = 15.2385 (8), c = 21.0682 (11) Å, V = 4174.1 (4) Å3,= 1.344 g cm–3, = 0.147 mm–1, T = 295 (2) K, orange cubes; 18962 independent measured reflections, F2 refinement, R1 = 0.1193, wR2 = 0.2629. 10. Using ITC competition experiments, we determined the association constants for the interactions of the molecular cage 1 with the threadlike salts 3•2PF6 and 4•2PF6 in CHCl3/CH3CN (1:1) to be 2.9 x 105 and 1. 7 x 106 M–1, respectively. 11. The binding selectivities of 21C7 and 24C8 (K21C7M+/K24C8M+) toward either Na+ or K+ ion in MeOH at 298 K are less than 10. see: (a) Frensdorff, H. K. J. Am. Chem. Soc. 1971, 93, 600–606. (b) Lamb, J. D.; Izatt, R. M.; Swain, C. S.; Christensen, J. J. J. Am. Chem. Soc. 1980, 102, 475–479. (c) Inoue, Y.; Liu, Y.; Tong, L.-H.; Ouchi, M.; Hakushi, T. J. Chem. Soc., Perkin Trans. 2, 1993, 1947–1950. 12. Hsu, C.-C.; Chen, N.-C.; Lai, C.-C.; Liu, Y.-H.; Peng, S.-M.; Chiu, S.-H. Angew. Chem. Int. Ed. 2008, 47, 7475–7478. 13. Under the same conditions, the addition of dipropargylammonium tetrafluoroborate to the solution did not result in clean or efficient switching. 14. (a) Kottas, G. S.; Clarke, L. I.; Horinek, D.; Michl, J. Chem. Rev. 2005, 105, 1281–1376. (b) Khuong, T. A. V.; Nunez, J. E.; Godinez, C. E.; Garcia-Garibay, M. A. Acc. Chem. Res. 2006, 39, 413–422. 15. (a) Bedard, T. C.; Moore, J. S. J. Am. Chem. Soc. 1995, 117, 10662–10671. (b) Hirata, O.; Takeuchi, M.; Shinkai, S. Chem. Commun. 2005, 3805–3807. (c) Alfonso, I.; Burguete, M. I.; Galindo, F.; Luis, S. V.; Vigara, L. J. Org. Chem. 2007, 72, 7947–7956. (d) Dominguez, Z.; Dang, H.; Strouse, M. J.; Garcia-Garibay, M. A. J. Am. Chem. Soc. 2002, 124, 2398–2399. (e) Setaka, W.; Ohmizu, S.; Kabuto, C.; Kira, M. Chem. Lett. 2007, 36, 1076–1077. (f) Nunez, J. E.; Natarajan, A.; Khan, S. I.; Garcia-Garibay, M. A. Org. Lett. 2007, 9, 3559–3561. 16. (a) Shima, T.; Hampel, F.; Gladysz, J. A. Angew. Chem. Int. Ed. 2004, 43, 5537–5540. (b) Wang, L.; Hampel, F.; Gladysz, J. A. Angew. Chem. Int. Ed. 2006, 45, 4372–4375. 17. Sokolov, A. N.; Swenson, D. C.; MacGillivray, L. R. Proc. Natl. Acad. Sci. USA 2008, 105, 1794–1797. 18. (a) Scarso, A.; Onagi, H.; Rebek, J., Jr. J. Am. Chem. Soc. 2004, 126, 12728–12729. (b) Kitagawa, H.; Kobori, Y.; Yamanaka, M.; Yoza, K.; Kobayashi, K. Proc. Natl. Acad. Sci. USA 2009, 106, 10444–10448. 19. (a) Zheng, X.; Mulcahy, M. E.; Horinek, D.; Galeotti, F.; Magnera, T. F.; Michl, J. J. Am. Chem. Soc. 2004, 126, 4540–4542. (b) Horinek, D.; Michl, J. Proc. Natl. Acad. Sci. USA 2005, 102, 14175–14180. 20. (a) Balzani, V.; Credi, A.; Raymo, F. M.; Stoddart, J. F. Angew. Chem. Int. Ed. 2000, 39, 3348–3391. (b) Cheng, K.-W.; Lai, C.¬-C.; Chiang, P.-T.; Chiu, S.-H. Chem. Commun. 2006, 2854–2856. (c) Kay, E. R.; Leigh, D. A.; Zerbetto, F. Angew. Chem. Int. Ed. 2007, 46, 72–191. (d) Champin, B.; Mobian, P.; Sauvage, J.-P. Chem. Soc. Rev. 2007, 36, 358–366. (e) Chuang, C.-J.; Li, W.-S.; Lai, C.-C.; Liu, Y.-H.; Peng, S.-M.; Chao, I.; Chiu, S.-H. Org. Lett. 2009, 11, 385–388. 21. (a) Lin, C.-F.; Liu, Y.-H.; Lai, C.-C.; Peng, S.-M.; Chiu, S.-H. Angew. Chem. Int. Ed. 2006, 45, 3176–3181. (b) Yen, M.-L.; Chen, N.-C.; Lai, C.-C.; Liu, Y.-H.; Peng, S.-M.; Chiu, S.-H. Org. Lett. 2009, 11, 4604–4607. 22. (a) Kasmai, H. S.; Mischke, S. G.; Blake, T. J. J. Org. Chem. 1995, 60, 2267–2270. (b) Lamsa, M.; Huuskonen, J.; Rissanen, K.; Pursiainen, J. Chem. Eur. J. 1998, 4, 84–92. (c) Chen, N.-C.; Huang, P.-Y.; Lai, C.-C.; Liu, Y.-H.; Wang, Y.; Peng, S.-M.; Chiu, S.-H. Chem. Commun. 2007, 4122–4124. 23. Bolitt, V.; Mioskowski, C.; Reddy, S. P.; Falck, J. R. Synthesis, 1988, 388–389. 24. Crystal data for [1•K23][2PF6]: [C72H82K2O18N2•2CHCl3•H2O][2PF6], Mr = 1886.27, triclinic, space group p-1, a = 9.3095 (10), b = 13.4294 (10), c = 17.4556 (15) Å,V = 2073.3 (3) Å3, = 1.511 g cm–3,(CuK= 3.994 mm–1, T = 150 (2) K, orange cube; 7490 independent measured reflections, F2 refinement, R1 = 0.1417, wR2 = 0.3387. 25. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nos. CCDC-768489 [1•K213][2PF6], and –768490 [113-H2][2CF3CO2]. Copies of the data can be obtained free of charge upon application to CCDC, 12 Union Road, Cambridge CB21EZ, UK [fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk] 26. Because of its electron-withdrawing C=O groups, the pyridyl units in the dione 13 are significantly less basic than pyridine itself. According to the signal shifts in the 1H NMR spectra upon titrating an equimolar mixture of the molecular cage 1 and the dione 13 with TFA in CDCl3/CD3CN (1:1), at least 20 equiv of TFA were required to protonate the guest completely. 27. Crystal data for [13-H2][2CF3CO2]: [C60H76O16•C12H8N2O2•CH2Cl2][2CF3CO2], Mr = 1576.38, triclinic, space group p-1, a = 12.3293 (4), b = 13.3179 (5), c = 13.9601 (5) Å, V = 2172.18 (14) Å3,= 1.205 g cm–3,) = 1.357 mm–1, T = 150 (2) K, orange column; 6981 independent measured reflections, F2 refinement, R1 = 0.1688, wR2 = 0.4053. 28. We estimated this value from the angles between (i) the axes defined by the two carbonyl groups of the anthraquinone guest and (ii) the planes defined by the four methyl groups of the host in the solid state structures of complexes (1•K23-H2)2+. Of course, the actual rotation might have any value defined by the expression 74° ± n180° (where n is an integer). 29. because the components of this complex are not mechanically interlocked, the rotation of the guest does not necessarily occur directly within the host–it may occur in solution through a process of decomplexation, rotation, and recomplexation (with associated/dissociated H+ and/or K+ ions in each step). We suspect, however, that a system in which the molecular cage and guest moieties were not free to disassemble, but where H+ and K+ ions could freely enter and exit the molecular cage through it crown ether-like cavities, would exhibit more-realistic gyroscopic motion. 30. Lin, C.-F.; Liu, Y.-H.; Lai, C.-C.; Peng, S.-M.; Chiu, S.-H Chem. Eur. J. 2006, 12, 4594–4599. 31. Hsu, C.-C.; Chen, N.-C.; Lai, C.-C.; Liu, Y.-H.; Peng, S.-M.; Chiu, S.-H. Angew. Chem. Int. Ed. 2008, 47, 7475–7478. 32. Krasia, T. C.; Steinke, J. H. G. Chem. Commun, 2002, 22–23. 33. Yamawaki, J.; Ando, T. Chem. Lett. 1980, 533–536. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/46110 | - |
| dc.description.abstract | 以分子籠 1作為主體分子，我們發展了一個獨特的主體/客體錯合系統。由於分子籠 1對鍵結雙偶氮陽離子、雙吡啶陽離子及蒽醌分子具有不同程度的錯合能力，因此在其混合溶液中分子籠 1僅會與雙偶氮陽離子鍵結產生穩定的錯合物而留下未錯合的雙吡啶陽離子及蒽醌分子。然而藉由適當的刺激操作，分子籠 1可以選擇性地改變其錯合的客體，而分別與雙偶氮陽離子、雙吡啶陽離子及蒽醌分子等三種不同種類之客體分子鍵結。此外，我們發現分子籠 1能夠鍵結客體分子2,6-diazaanthracene-9,10-dione 13於其內部空腔中。由於客體分子2,6-diazaanthracene-9,10-dione 13羰基上的氧原子能與鉀離子配位，因此我們可以藉由加入和移除鉀離子來控制客體分子 2,6-diazaanthracene-9,10-dione 13在分子籠 1空腔內進行類似旋轉的運動，而這樣的運動模式或許可在某種程度上可以模擬一個分子迴轉儀的運轉。 | zh_TW |
| dc.description.abstract | Herein, we have demonstrated a crown ether based molecular cage 1 that forms extremely stable supramolecular complexes with bisdiazonium ions in solution. A system based on a molecular cage, in which bisdiazonium, bispyridinium, and anthraquinone guests can be complexed to the host sequentially through the application of suitable stimuli, is reported.We have demonstrated that the molecular cage 1 can complex the guest 2,6-diazaanthracene-9,10-dione 13 in its internal cavity. This complex may mimic the function of a molecular gyroscope in that its complexed guest changes its binding geometry with respect to the macrocyclic host upon the addition and removal of K+ ions. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-15T04:54:16Z (GMT). No. of bitstreams: 1 ntu-99-D95223021-1.pdf: 6337519 bytes, checksum: bc6bb4da936cf47a2579dfc1a2e64aa0 (MD5) Previous issue date: 2010 | en |
| dc.description.tableofcontents | 摘 要……………………………………………………………………...I
論 文 發 表………..…………………………………………………..III 目 錄……..…………………………………………..…………………IV 流 程 目 錄…..………………………………………………………..VI 圖 表 目 錄……..…………………………………………………….VII Chapter 1 利用分子籠在溶液中可選擇性鍵結三種不同種類客體分子之研究…………………………………………………………………1 1.1 研究動機………………………………………………………… 2 1.2 探討偶氮陽離子與分子籠 1之間的錯合行為………………….4 1.3 尋找合適客體分子及控制試劑………………………..………...9 1.4 探討分子籠 1選擇鍵結三種不同類型客體分子……………...14 1.5 結論……………………………………………………………...22 Chapter 2 控制已錯合客體分子在分子籠空腔內進行旋轉運動之研究….…………………………………………………………………….23 2.1 研究動機………………………….………………...…………...24 2.2 尋找合適的客體分子…………………………………………...26 2.3 探討dione 13與分子籠 1之間的錯合行為………...………….32 2.4 探討dione 13與分子籠 1之間的旋轉運動................................37 2.5 結論……………………………………………………………...40 實驗部份………………………………………………………………..41 參考文獻………………………………………………………………. 56 附 錄：Job plot與結合常數測量及2D NMR 1H與13C核磁共振光譜………...…………………………………………………………….. 64 | |
| dc.language.iso | zh-TW | |
| dc.subject | 分子開關 | zh_TW |
| dc.subject | molecular switch | en |
| dc.title | 以籠狀冠醚分子為架構的分子開關與分子機械之研究 | zh_TW |
| dc.title | From Molecular Cage towards Molecular Switches and Molecular Machines | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 98-2 | |
| dc.description.degree | 博士 | |
| dc.contributor.oralexamcommittee | 陳平(Richard P. Cheng),徐秀福(Hsiu-Fu Hsu),黃暄益(Michael H. Huang),賴建成(Chien-Chen Lai),翁紹華(Shau-Hua Ueng) | |
| dc.subject.keyword | 分子開關, | zh_TW |
| dc.subject.keyword | molecular switch, | en |
| dc.relation.page | 65 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2010-07-30 | |
| 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 | |
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