DC Field | Value | Language |
---|---|---|
dc.contributor.advisor | Shim, Sang-Chul | - |
dc.contributor.advisor | 심상철 | - |
dc.contributor.author | Lee, Tae-Suk | - |
dc.contributor.author | 이태석 | - |
dc.date.accessioned | 2011-12-13T04:24:58Z | - |
dc.date.available | 2011-12-13T04:24:58Z | - |
dc.date.issued | 1988 | - |
dc.identifier.uri | http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=61128&flag=dissertation | - |
dc.identifier.uri | http://hdl.handle.net/10203/31298 | - |
dc.description | 학위논문(박사) - 한국과학기술원 : 화학과, 1988.2, [ xxii, 185 p. ] | - |
dc.description.abstract | Several aryl 1,3,5-hexatriynes were synthesized by the use of 1-aryl-4-trimethylsilyl-1,3-butadiyne intermediates. 1-Phenyl-1,3,5-heptatriyne and 1-(1``-naphthyl)-1,3,5-heptatriyne were prepared by the use of 1-trimethylsilyl-1,3-pentadiyne which is a very stable precursor for the 1,3-pentadiyne at room temperature. 1-Phenyl-6-tbutyldimethylsilyl-1,3,5-hexatriyne was synthesized by Cadiot-Chodkiewicz coupling reaction and 1-phenyl-1,3,5-hexatriyne was synthesized by desilylation of 1-phenyl-6-tbutyldimethylsilyl-1,3,5-hexatriyne. Fluorescence quantum yields and phosphorescence lifetimes were measured for the synthetic polyacetylenes. 1-Aryl-1,3butadiynes, $\underline{1}-\underline{6}$ were photolyzed in 2,3-dimethyl-2-butene to obtain [2+2] type photocycloadducts $\underline{16}-\underline{21}$ except for $\underline{5}$ which yields two photoadducts. Azulene quenching, fluorescence, and exciplex emission studies suggest for $\underline{1}-\underline{4}$ that the reaction proceeds from both singlet and triplet excited states but not through the singlet exciplex formation with olefins, and for 5 and 6 the reaction proceeds from the triplet excited state. Photolysis of 1-phenyl-1,3,5- hexatriynes, $\underline{9}-\underline{12}$ in deaerated 2,3-dimethyl-2butene gave bicyclopropyl photoadducts, $\underline{23}-\underline{27}$. No photoadduct was formed with aerated 2,3-dimethyl-2-butene or deaerated solutions of dimethyl fumarate, methyl crotonate, dimethyl maleate, $\underline{\mbox{trans}}$-1,2-dichloroethylene, and acrylonitrile, while, 1,6-diphenyl1,3,5-hexatriyne in deaerated 2,3-dimethyl-2-butene/acrylonitrile (1:1 molar ratio) cosolvent system yielded the photoadducts $\underline{23}$ and $\underline{28}$. A plausible reaction mechanism involving electron delocalized triplet state (1,6-diradical type) and carbene intermediate was proposed. The irradiation of -naphthyl-1, 3-butadiynes, $\underline{2}-\underline{4}$ in aqueous sulfuric acid yields two photohy... | eng |
dc.language | eng | - |
dc.publisher | 한국과학기술원 | - |
dc.title | Photochemistry of conjugated polyacetylenes | - |
dc.title.alternative | 콘주게이트된 폴리아세틸렌들의 광화학 | - |
dc.type | Thesis(Ph.D) | - |
dc.identifier.CNRN | 61128/325007 | - |
dc.description.department | 한국과학기술원 : 화학과, | - |
dc.identifier.uid | 000845262 | - |
dc.contributor.localauthor | Shim, Sang-Chul | - |
dc.contributor.localauthor | 심상철 | - |
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