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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 陸天堯(Tien-Yau Luh) | |
| dc.contributor.author | Yi-Chung Dzeng | en |
| dc.contributor.author | 曾益中 | zh_TW |
| dc.date.accessioned | 2021-05-14T17:42:26Z | - |
| dc.date.available | 2015-08-20 | |
| dc.date.available | 2021-05-14T17:42:26Z | - |
| dc.date.copyright | 2015-08-20 | |
| dc.date.issued | 2015 | |
| dc.date.submitted | 2015-08-17 | |
| dc.identifier.citation | 1. (a) Colvin, E. W. Silicon Reagents in Organic Synthesis; Academic: San Diego, USA, 1988; pp 1 – 5. (b) Corey, J. Y. Historical overview and comparison of silicon with carbon. In The Chemistry of Organic Silicon Compounds, Volume 1; Patai, S; Rappoport, Z., Ed.; John Wiley & Sons, Ltd, Chichester, UK, 1989; pp 1–101. (c) Cartledge, R. K. Journal of Organometallic Chemistry, 1982, 225, 131–139.
2. For reviews: (a) Miller, R. D.; Michl, J. Chem. Rev. 1989, 89, 1359–1410. (b) Raabe, G.; Michl, J. Chem. Rev. 1985, 85, 419–509. (c) West, R.; West, R. Polyhedron 2002, 21, 467–472. (d) Tokitoh, N. and Okazaki, R. Recent Advances in the Chemistry of Silicon–Heteroatom Multiple Bonds. In The Chemistry of Organic Silicon Compounds, Volume 2; Rappoport, Z.; Apeloig, Y., Ed.; John Wiley & Sons, Ltd: Chichester, UK, 1998; pp 1063 - 1103. 3. (a) West, R.; Fink, M. J.; Michl, J. Science 1981, 214, 1343–1344. (b) Sekiguchi, A.; Kinjo, R.; Ichinohe, M. Science 2004, 305, 1755–1757. (c) Wiberg, N.; Finger, C. M. M.; Polborn, K. Angew. Chem., Int. Ed. Engl. 1993, 32, 1054-1056. (d) Kipping, F. S. J. Chem. Soc., Trans., 1921, 119, 647-653 (e) Ishida, S.; Iwamoto, T.; Kabuto, C.; Kira, M. Nature 2003, 421, 725 - 727. 4. Fleming, I.; Dunoguès, J.; Smithers, R. The Electrophilic Substitution of Allylsilanes and Vinylsilanes In Organic Reactions; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2004; pp 57–575. 5. (a) West, R.; David, L. D.; Djurovich, P. I.; Stearley, K. L.; Srinivasan, K. S. V; Yu, H. J. Am. Chem. Soc. 1981, 103, 7352–7354. (b) Sakurai, H.; Kira, M.; Uchida, T. J. Am. Chem. Soc. 1973, 95, 6826-6827. (c) Chicart, P.; Corriu, R. J. P.; Moreau, J. J. E.; Garnier, F.; Yassar, A. Chem. Mater. 1991, 3, 8-10. (d) Ohshita, J.; Kanaya, D.; Ishikawa, M.; Koike, T.; Yamanaka, T. Macromolecules 1991, 24, 2106-2107. (e) Sakurai, H.; Sakamoto, K.; Kira, M. Chemistry Letters, 1984, 1213–1214. (f) Sakurai, H.; Sakamoto, K.; Kira, M. Chemistry Letters, 1984, 1213–1214. (g) Corriu, R. J. P.; Guerin, C.; Henner, B.; Kuhlmann, T. Organometallics 1990, 351–352. (h) Ijadi-Maghsoodi, S.; Barton, T. J. Macromolecules 1990, 23, 4485–4486. 6. (a) Shizuka, H.; Obuchi, H.; Ishikawa, M.; Kumada, M. J. Chem. Soc. Chem. Commun. 1981, 405. (b) Sakurai, H.; Sugiyama, H.; Kira, M. J. Phys. Chem. 1990, 94, 1837–1843. (c) Fang, M.; Watanabe, A.; Matsuda, M. Macromolecules 1996, 29, 6807–6813. (d) Kwak, G.; Masuda, T. Macromolecules 2002, 35, 4138–4142. (e) Brown, A. E.; Eichler, B. E. Tetrahedron Lett. 2011, 52, 1960–1963. (f) Shimizu, M.; Kawaguchi, T.; Oda, K.; Hiyama, T. Chem. Lett. 2007, 36, 412–413. 7. (a) Sakurai, H.; Kira, M.; Uchida, T. J. Am. Chem. Soc. 1973, 95, 6826–6827. (b) Ishikawa, M.; Hatano, T.; Hasegawa, Y.; Horio, T.; Kunai, A.; Miyai, A.; Ishida, T.; Tsukihara, T.; Yamanaka, T. Organometallics 1992, 11, 1604 - 1618. (c) Oshita, J.; Takada, A.; Kunai, A.; Komaguchi, K.; Shiotani, M.; Adachi, A.; Sakamaki, K.; Okita, K.; Harima, Y.; Konugi, Y.; Yamashita K.; Ishikawa, M. Organometallics 2000, 19, 4492-4498. (d) Fang, M.; Watanabe, A.; Matsuda, M. Macromolecules 1996, 29 , 6807 - 6813. (e) Kwak, G.; Masuda, T. Macromolecules 2002, 35, 4138 - 4142. (f) Kwak, G.; Masuda, T. Macromol. Rapid Commun. 2001, 22, 846 - 849. 8. (a) van Walree, C. A.; Roest, M. R.; Schuddeboom, W.; Jejnneskens, L. W.; Verhoeven, J. W.; Warman, J. M.; Kooijman, H.; Spek, A. L. J. Am. Chem. Soc. 1996, 118, 8395-8407. (b) Van Walree, C. A.; Kooijman, H.; Spek, A. L.; Zwikker, J. W.; Jenneskens, L. W. J. Chem. Soc. Chem. Commun. 1995, No. 1, 35. (c) Zehnacker, A.; Lahmani, F.; van Walree, C. A.; Jenneskens, L. W. J. Phys. Chem. A 2000, 104, 1377–1387. 9. (a) Burroughes, J. H.; Bradley, D. D. C.; Brown, a. R.; Marks, R. N.; Mackay, K.; Friend, R. H.; Burns, P. L.; Holmes, a. B. Nature 1990, 347, 539–541. (b) Grimsdale, A. C.; Chan, K. L.; Martin, R. E.; Jokisz, P. G.; Holmes, A. B. Chem. Rev. 2009, 109, 897–1091. (c) Bunz, U. H. F. Chem. Rev. 2000, 100, 1605–1644. (d) Martin, R. E.; Diederich, F. Angew. Chemie Int. Ed. 1999, 38, 1350–1377. 10. (a) Brouwer, H. J.; Krasnikov, V. V; Hilberer, a; Hadziioannou, G. Adv. Mater. 1996, 8, 935–937. (b) Kim, H. K.; Ryu, M.; Lee, S. Macromolecules 1997, 30, 1236–1239. (c) Gao, Z.; Lee, C. S.; Bello, I.; Lee, S. T.; Chen, R.-M.; Luh, T.-Y.; Shi, J.; Tang, C. W. Appl. Phys. Lett. 1999, 74, 865. 11. (a) Chen, R.-M.; Chien, K.-M.; Wong, K.-T.; Jin, B.-Y.; Luh, T.-Y.; Hsu, J.-H.; Fann, W. J. Am. Chem. Soc. 1997, 119, 11321-11322. (b) Chen, R.-M.; Luh, T.-Y. Tetrahedron 1998, 54, 1197–1206. (c) Yeh, M.-Y.; Lin, H.-C.; Lee, S.-L.; Chen, C.-H.; Lim, T.-S.; Fann, W.; Luh, T.-Y. Chem. Commun. 2007, 3459-3461. 12. (a) Cheng, Y.-J.; Hwu, T.-Y.; Hsu, J.-H.; Luh, T.-Y. Chem. Commun. 2002, 1978–1979. (b) Cheng, Y.-J.; Luh, T.-Y. Chem. Eur. J. 2004, 10, 5361–5368. (c) Luh, T.-Y.; Cheng, Y.-J. Chem. Commun. 2006, 4669–4678. (d) Cheng, Y.-J.; Basu, S.; Luo, S.-J.; Luh, T.-Y. Macromolecules 2005, 38, 1442–1446. 13. (a) Yeh, M. Y.; Lin, H. C.; Lim, T. S.; Lee, S. L.; Chen, C. H.; Fann, W.; Luh, T. Y. Macromolecules 2007, 40, 9238–9243. (b) Chen, C.-H.; Huang, Y.-C.; Liao, W.-C.; Lim, T.-S.; Liu, K.-L.; Chen, I.-C.; Luh, T.-Y. Chem. Eur. J. 2012, 18, 334–346. (c) Liao, W.-C.; Chen, W.-H.; Chen, C.-H.; Lim, T.-S.; Luh, T.-Y. Macromolecules 2013, 46, 1305-1311. (d) Chen, C.-H.; Chen, W.-H.; Liu, Y.-H.; Lim, T.-S.; Luh, T.-Y. Chem. Eur. J. 2012, 18, 347–354. 14. For reviews, see: (a) Jung, M. E.; Piizi, G. Chem. Rev. 2005, 105, 1735-1766. (b) Sammes, P. G.; Weller, D. J. Synthesis 1995, 1205-1222. (c) Galli, C.; Mandolini, L. Eur. J. Org. Chem. 2000, 3117-3125 (d) Luh, T.-Y.; Hu, Z. Dalton Trans. 2010, 39, 9185-9192. (e) Toniolo, C.; Crisma, M.; Formaggio, F.; Peggion, C. Biopolymers 2001, 60, 396-419. 15. (a) Beesley, R. M.; Ingold, C. K.; Thorpe, J. F. J. Chem. Soc. Trans. 1915, 107, 1080. (b) Ingold, C. K.; Sako, S.; Thorpe, J. F. J. Chem. Soc. Trans. 1922, 121, 1177. 16. (a) Kirby, A. J.; Lancaster, P. W. J. Chem. Soc. Perkin Trans. 2 1972, 1206-1214. (b) Kirby, A. J.; Lloyd, G. J. J. Chem. Soc. Perkin Trans. 2 1976, 1753-1761. (c) Jager, J.; Graafland, T.; Schenk, H.; Kirby, A. J.; Engberts, J. B. F. N. J. Am. Chem. Soc. 1984, 106, 139-143. (d) Kirby, A. J. Adv. Phys. Org. Chem. 1994, 29, 87-183. 17. (a) Sternbach, D. D.; Rossana, D. M. Tetrahedron Lett. 1982, 23, 303–306. (b) Sternbach, D. D.; Rossana, D. M.; Onan, K. D. Tetrahedron Lett. 1985, 26, 591–594. 18. Bunz, U. H. F. Top. Curr. Chem. 1999, 201, 131–161. 19. Bothner-By, A.A.; Colin, C. N.; Günther, H. J. Am. Chem. Soc. 1962, 84, 2748-2751. 20. 葉美鈺，國立臺灣大學化學所博士論文，2007. 21. (a) Tsuji, J. Palladium Reagents and Catalysts: New Perspectives for the 21st Century; John Wiley & Sons, Ltd: Chichester, UK, 2005; pp. 543-563.(b) Elsevier, C. J.; Kleijn, H.; Ruitenberg, K.; Vermeer, P. J. Chem. Soc. Chem. Commun. 1983, 1529-1530. 22. Alberts, A. H. J. Am. Chem. Soc. 1989, 111, 3093-3094. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/4462 | - |
| dc.description.abstract | Alternating tert-butyl- and methyl- substituted alkoxymethylene-diethynylbenzene copolymers 11 with different degree of polymerization and the corresponding dimers 15 were synthesized. The tert-butyl substituted polymers 11b show strong emissions around 350-400 due to ground state interactions between adjacent chromophores while copolymer 11a with less bulkily methyl-substituted tether exhibits emission around 400-450 nm due to through-space interactions between nonadjacent diethynylbenzene chromophores. Such substituent effect on photophysical properties was attributed to the Thorpe-Ingold effect exerted by the bulky tert-butyl group, compressing the bond angle at the methylene tether and therefore altering the overall folding behavior of the polymer chain. As the polymer chains fold in different manner, difference in intrachain chromophore-chromophore interaction modes were expected and corresponding photophysical property differences were observed.
These methylene tethered polymers have photophysical properties similar to those of the related silylene-tethered copolymers 1, albeit the relative intensity in the blue light emission is significantly smaller in methylene-bridged copolymers than in silylene-linked copolymers. Comparison between these two series of polymers suggests that folding behaviors of such polymers may depend on the tetrahedral tethers (methylene versus silylene). | en |
| dc.description.provenance | Made available in DSpace on 2021-05-14T17:42:26Z (GMT). No. of bitstreams: 1 ntu-104-R02223185-1.pdf: 6140695 bytes, checksum: e3d6a13049bd09e0a2e9a172ce3c40b8 (MD5) Previous issue date: 2015 | en |
| dc.description.tableofcontents | Acknowledgements I
Abstract II Table of Contents III List of Tables V List of Figures VI Chapter 1: Introduction 1-19 1.1 Carbon v.s. Silicon 1 1.1.1 Reactivities 1.1.2 Silicon containing conducting polymers 1.1.3 The Si - interactions to connected chromophores6 1.1.4 The interaction of chromophore across a single atom bridge: C versus Si 1.2 Alternating copolymers containing monosilylene spaced chromophores 8 1.2.1 SiR2-Ar copolymers as electro-optical materials 1.2.2 Photophysical properties of alternating dialkylsilylene-divinylbenzene copolymers: ground state interactions 1.2.3 Chromophore-chromophore interactions and conjugation length 1.2.4 Intrachain Energy transfer in silylene-divinylarene copolymers 1.2.5 -Intrachain Photoinduced electron transfer 1.2.6 Role of polymer conformations in interchromophore interactions 1.3 Thorpe-Ingold effect 16 1.3.1 A summary 1.3.2 Thorpe-Ingold effect in dialkylsilylene containing polymers Chapter 2: Results and discussion 20-37 2.1 Design and synthesis: a carbon version of polymer 1 20 2.1.1 Design of polymer 11 2.1.2 Synthesis, Purification and Characterization of polymer 11 2.1.3 Synthesis of diynes 13a and 13b 2.1.4 Synthesis of monomer 14 and dimers 15 2.2 Steady-State Photophysical Properties. 28 2.2.1 UV-Vis Absorption Spectroscopy 2.2.2 Fluorescence spectroscopy 2.2.3 Excitation spectra 2.3 Time-resolve fluorescence spectroscopy 33 2.3.1 Monomer and Dimers 2.3.2 Polymers with methyl substituent 2.3.3 Polymers with t-Bu substituent Chapter 3: Conclusions 38-41 Chapter 4: Experimental Sections 38-41 4.1 General 42 4.2 Synthesis 43 4.3 Steady State Photophysical measurements 52 4.4 Time Resolved Fluorescence Measurements. 53 Chapter 5: References 54-57 Appendix I. 1H and 13C NMR spectra of new compounds. 58-88 Appendix II. GPC chromatograms of polymers 6. 89-90 Appendix III. Time-resolved fluorescence decay profiles. 91-93 | |
| dc.language.iso | en | |
| dc.title | 亞甲基-二乙炔苯共聚物光物理性質之取代基效應：比較亞甲基及矽代亞甲基連接基團對對高分子摺疊之影響 | zh_TW |
| dc.title | Unusual Substituent-Dependent Photophysical Properties of Alternating Substituted Methylene-Diethynylbenzene Copolymers: a Comparison of Methylene versus Silylene Tethers on Polymer Folding | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 103-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 梁文傑(Man-kit Leung),鄭彥如(Yen-Ju Cheng),詹益慈(Yi-Tsu Chan) | |
| dc.subject.keyword | 聚合物,光物理,摺疊,發光團,分子內作用,Thorpe-Ingold作用,構型, | zh_TW |
| dc.subject.keyword | Polymer,Photophysics,Folding,Chromophore,Intramolecular interaction,Thorpe-Ingold effect,conformation, | en |
| dc.relation.page | 93 | |
| dc.rights.note | 同意授權(全球公開) | |
| dc.date.accepted | 2015-08-17 | |
| 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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