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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 邱靜雯(Ching-Wen Chiu) | |
| dc.contributor.author | Meng-Ting Chang | en |
| dc.contributor.author | 張孟庭 | zh_TW |
| dc.date.accessioned | 2021-06-16T23:41:51Z | - |
| dc.date.available | 2017-07-31 | |
| dc.date.copyright | 2012-07-31 | |
| dc.date.issued | 2012 | |
| dc.date.submitted | 2012-07-25 | |
| dc.identifier.citation | 1. (a) Kitagawa, S.; Kitaura, R.; Noro, S.-i. Angew. Chem. Int. Ed. 2004, 43 (18), 2334-2375; (b) Long, J. R.; Yaghi, O. M. Chem. Soc. Rev. 2009, 38 (5), 1213-1214.
2. Kitagawa, S.; Matsuda, R. Coord. Chem. Rev. 2007, 251 (21–24), 2490-2509. 3. Furukawa, H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S. B.; Choi, E.; Yazaydin, A. O.; Snurr, R. Q.; O’Keeffe, M.; Kim, J.; Yaghi, O. M. Science 2010, 329 (5990), 424-428. 4. Suh, M. P.; Park, H. J.; Prasad, T. K.; Lim, D.-W. Chem. Rev. 2011, 112 (2), 782-835. 5. Furukawa, H.; Yaghi, O. M. J. Am. Chem. Soc. 2009, 131 (25), 8875-8883. 6. Millward, A. R.; Yaghi, O. M. J. Am. Chem. Soc. 2005, 127 (51), 17998-17999. 7. McDonald, T. M.; Lee, W. R.; Mason, J. A.; Wiers, B. M.; Hong, C. S.; Long, J. Am. Chem. Soc. 2012, 134 (16), 7056-7065. 8. Phan, A.; Czaja, A. U.; Gandara, F.; Knobler, C. B.; Yaghi, O. M. Inorg. Chem. 2011, 50 (16), 7388-7390. 9. Falkowski, J. M.; Wang, C.; Liu, S.; Lin, W. Angew. Chem. Int. Ed. 2011, 50 (37), 8674-8678. 10. Ma, L.; Falkowski, J. M.; Abney, C.; Lin, W. Nat. Chem. 2010, 2 (10), 838-846. 11. Wanzlick, H. W. Angew. Chem. Int. Ed., 1962, 74 (4), 129-134. 12. Wanzlick, H. W.; Schonherr, H. J. Angew. Chem. Int. Ed. 1968, 80 (4), 154-154. 13. Arduengo, A. J.; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1991, 113 (1), 361-363. 14. Dorta, R.; Stevens, E. D.; Scott, N. M.; Costabile, C.; Cavallo, L.; Hoff, C. D.; Nolan, S. P. J. Am. Chem. Soc. 2005, 127 (8), 2485-2495. 15. Zhang, C.; Huang, J.; Trudell, M. L.; Nolan, S. P. J. Org. Chem. 1999, 64 (11), 3804-3805. 16. Andrus, M. B.; Song, C. Org. Lett. 2001, 3 (23), 3761-3764. 17. (a) Stauffer, S. R.; Lee, S.; Stambuli, J. P.; Hauck, S. I.; Hartwig, J. F. Org. Lett. 2000, 2 (10), 1423-1426; (b) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem. 2002, 67 (16), 5553-5566. 18. Sohn, S. S.; Rosen, E. L.; Bode, J. W. J. Am. Chem. Soc. 2004, 126 (44), 14370-14371. 19. Fukuda, Y. M., Y.; Ishii, S.; Kondo, K.; Aoyama, Synthesis 2006, 589. 20. (a) Grasa, G. A. K., R. M.; Nolan, S. P., Org. Lett. 2002, 4, 3583; (b) Nyce, G. W. L., J. A.; Connor, E. F.; Waymouth,; R. M.; Hedrick, J. L., Org. Lett. 2002, 4, 3583; (c) Grasa, G. A.; Guveli, T. S., R.; Nolan, S. P., J. Org. Chem. 2003, 68, 2812. 21. Benhamou, L.; Chardon, E.; Lavigne, G.; Bellemin-Laponnaz, S. p.; Cesar, V. Chem. Rev. 2011, 111 (4), 2705-2733. 22. Kuhn, K. M.; Grubbs, R. H. Org. Lett. 2008, 10 (10), 2075-2077. 23. Sanderson, M. D.; Kamplain, J. W.; Bielawski, C. W. J. Am. Chem. Soc. 2006, 128 (51), 16514-16515. 24. Rit, A.; Pape, T.; Hepp, A.; Hahn, F. E. Organometallics 2010, 30 (2), 334-347. 25. Boydston, A. J.; Williams, K. A.; Bielawski, C. W. J. Am. Chem. Soc. 2005, 127 (36), 12496-12497. 26. Williams, K. A.; Bielawski, C. W. Chem. Commum. 2010, 46 (28), 5166-5168. 27. Boydston, A. J.; Pecinovsky, C. S.; Chao, S. T.; Bielawski, C. W. J. Am. Chem. Soc. 2007, 129 (47), 14550-14551. 28. Inokuma, Y.; Arai, T.; Fujita, M. Nat. Chem. 2010, 2 (9), 780-783. 29. Morris, W.; Leung, B.; Furukawa, H.; Yaghi, O. K.; He, N.; Hayashi, H.; Houndonougbo, Y.; Asta, M.; Laird, B. B.; Yaghi, O. M. J. Am. Chem. Soc. 2010, 132 (32), 11006-11008. 30. Oisaki, K.; Li, Q.; Furukawa, H.; Czaja, A. U.; Yaghi, O. M. J. Am. Chem. Soc. 2010, 132 (27), 9262-9264. 31. Chun, J.; Jung, I. G.; Kim, H. J.; Park, M.; Lah, M. S.; Son, S. U. Inorg. Chem. 2009, 48 (14), 6353-6355. 32. Choi, J.; Yang, H. Y.; Kim, H. J.; Son, S. U. Angew. Chem. Int. Ed., 2010, 49 (42), 7718-7722. 33. Jahnke, F. E. H. a. M. C., Angew. Chem. Int. Ed. 2008, 47, 3122. 34. Levell, J. W.; Ruseckas, A.; Henry, J. B.; Wang, Y.; Stretton, A. D.; Mount, A. R.; Galow, T. H.; Samuel, I. D. W. J. Phys. Chem. A 2010, 114 (51), 13291-13295. 35. Todd W. Hudnall, A. G. T., and Christopher W. Bielawski*, Organometallics 2010, 29, 4569. 36. Chen, L.; Kim, J.; Ishizuka, T.; Honsho, Y.; Saeki, A.; Seki, S.; Ihee, H.; Jiang, D. J. Am. Chem. Soc. 2009, 131 (21), 7287-7292. 37. Murray V. Baker, Organometallics 2009, 28, 3793–3803. 38. Qing-Xiang Liu, Polyhedron 2008, 27, 87–94. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/65420 | - |
| dc.description.abstract | 為了研究聚碳烯在有機金屬聚合物之應用，我們合成一系列以三亞苯為基底具有不同取代基的三咪唑鹽，在4b的情形下可以得到穩定的三碳烯；在4a的情形下可以透過硫脲證明三碳烯中間體的存在。三咪唑鹽可與銠金屬離子、碘化銅及醋酸銀生成三碳烯金屬錯合物。三硫脲可透過三氟酸酐氧化生成雙硫鍵而得到聚合物；三咪唑鹽可以配位銀或汞離子生成配位聚合物。 | zh_TW |
| dc.description.abstract | Recent development of poly-NHCs reveals their potential application in constructing organic and organometallic polymers. In order to contribute to the field, we synthesized a series of planar trisimidazolium salts, the apparent precursor for tris(NHC)s, based on the triphenylene backbone. These imidazolium salts with D3h symmetry are prepared in moderate yield with various bulky N-substituents. Among these imidazolium salts, the t-butyl substituted free carbene (4b) was generated via deprotonation of [4b-H3]3+ with LDA. For the diphenylmethyl substituted one, [4a-H3]3+, a tris-thiourea derivative (4a-S3) isolated from the reaction of [4a-H3]3+, K2CO3, and S8 suggests the generation of the free carbene intermediate. Compound 4a-S3 can be further converted into poly-cationic disulfide salt with triflic anhydride, which acts as an oxidizing agent for thioureas. Reactions of [4a-H3]3+ and Ag2O or Hg(OAc)2 yield the polymeric Ag-NHC polymer and Hg-NHC polymer, respectively. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-16T23:41:51Z (GMT). No. of bitstreams: 1 ntu-101-R99223158-1.pdf: 4034636 bytes, checksum: 7818c16eb6e49d5ab0642114bd0fd2a6 (MD5) Previous issue date: 2012 | en |
| dc.description.tableofcontents | List of Figures……………………………………………………………………VI
List of Schemes……………………………………………………………………IX List of Tables………………………………………………………………………XI Chapter1. Backgrounds and Research Objective……………………………………1 1. Metal-Organic-Frameworks (MOFs)………………………………………1 I. Backgrounds……………………………………………………………1 II. Application of MOFs……………………………………………………8 2. N-heterocyclic Carbenes (NHCs)…………………………………………17 I. Backgrounds and properties……………………………………………17 II. Common synthetic methods for imidazolium salts (the apparent precursor for NHCs)s……………………………………………………………22 III. Poly-carbenes…………………………………………………………25 3. Research Objectives………………………………………………………29 Chapter2. Triphenylene-based Tri-N-heterocyclic Carbenes: syntheses and reactivity studies………………………………………………………………………………34 1. Ligand Design…………………………………………………………34 2. Result and Discussion……………………………………………………35 I. Synthesis of and structure of trisimidazolium with bulkyl groups……35 II. Synthesis of and structure of trisimidazolium with small groups……39 III. Synthesis of and structure of free-carbenes…………………………40 IV. Synthesis of and structure of tris-NHC metal complexes……………42 V. Photophysical Properties of trisimidazolium salts with different substituted groups……………………………………………………46 VI. Electrochemistry of the tri-Rh complex………………………………50 3. Experimental Section………………………………………………………51 I. General Considerations………………………………………………51 II. Synthesis……………………………………………………………52 Chapter3. Coordination polymers with carbene ligands……………………………61 1. Model studies………………………………………………………………61 2. Coordination polymers of 4a………………………………………………65 I. Coordination polymers with Hexakis(diphenylmethyl) triphenyltris(imidazolium) tetrafluoroborate [4a-H3]3+ as ligand……65 3. Poly-cationic disulfide polymer……………………………………………69 I. Poly-cationic disulfide salt with tris-thiourea (4a-S3) and triflic anhydride……………………………………………………………69 4. Experimental Section………………………………………………………72 I. General Considerations………………………………………………72 II. Synthesis……………………………………………………………73 Conclusions…………………………………………………………………………77 References……………………………………………………………………………78 Crystal data…………………………………………………………………………82 | |
| dc.language.iso | en | |
| dc.subject | 聚碳烯 | zh_TW |
| dc.subject | 有機金屬聚合物 | zh_TW |
| dc.subject | 三亞苯 | zh_TW |
| dc.subject | 三咪唑鹽 | zh_TW |
| dc.subject | 硫脲 | zh_TW |
| dc.subject | 三碳烯金屬錯合物 | zh_TW |
| dc.subject | 配位聚合物 | zh_TW |
| dc.subject | Hg-NHC polymer | en |
| dc.subject | Poly-NHCs | en |
| dc.subject | organometallic polymers | en |
| dc.subject | trisimidazolium salts | en |
| dc.subject | thiourea | en |
| dc.subject | Ag-NHC polymer | en |
| dc.subject | triphenylene | en |
| dc.title | 三亞苯三碳烯之合成及配位聚合物之應用 | zh_TW |
| dc.title | Triphenylene-based Tris-N-heterocyclic Carbenes: Syntheses, Reactivity Studies and the Corresponding Coordination Polymers | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 100-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 王渝(Wang Yu),王朝諺(Tiow-Gan Ong) | |
| dc.subject.keyword | 聚碳烯,有機金屬聚合物,三亞苯,三咪唑鹽,硫脲,三碳烯金屬錯合物,配位聚合物, | zh_TW |
| dc.subject.keyword | Poly-NHCs,organometallic polymers,triphenylene,trisimidazolium salts,thiourea,Ag-NHC polymer,Hg-NHC polymer, | en |
| dc.relation.page | 85 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2012-07-25 | |
| 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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