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研究生: 蔡麗蓉
TSAI, Li-Rong
論文名稱: 1,2-■■酮於凝相中之光物理性質及與四甲基乙烯光加成反應之研究
The Photophysical Properties of Aceanthrenequinone in Condense
指導教授: 方泰山
Fang, Tai-Shan
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
畢業學年度: 81
語文別: 中文
論文頁數: 90
中文關鍵詞: 1,2-■■酮;光物理;光加成反應
論文種類: 學術論文
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  • 1,2-■■酮於有機凝相中的吸收光譜顯示, 在約363 nm及 395 nm左右有
    兩帶主要之吸收峰, 吸收係數約在10~10之範圍 , 且具紅位移性質, 故
    其最低激發單態為(π,π*)。在450 nm至650 nm間有螢光放射, 但無可測
    得之磷光 利用做為比對劑, 於環己烷,四氯化碳、苯及甲醇中測得各螢
    光量子產率值分別為0.15、0.02、0.019及0.0045,呈現出相當明顯之溶劑
    效應。根據焠熄原理,利用Stern-Volmer理論式,求得螢光之生命期約
    為9.8 ns。 1,2-■■酮與四甲基乙烯在去氧情況下於苯中照光, 約八小
    時後,可生成兩種主要產物:一為黃色之1,2光加成產物oxetane2 , 產率
    約為15%;另一則為紫黑色之1,4光加成產物dioxene3, 產率僅約3%。若以
    二苯甲酮做為敏光劑,黃色化合物之產率可提升至約35%左右。經以上1,2-
    ■■酮的吸收光譜,光激發光光譜、焠熄效應及光敏化反應等結果之分
    析, 兩主產物皆可能是由1,2-■■酮分子之T(n,π*)能階參與反應所生
    成。

    The absorption spectrum of aceanthrenequinone,1, in non-polar
    solvent shows a composition of two bands peaking at 363 nm and
    395 nm with absorption coefficients 1000 ~ 10000. The red
    shift of both bands in polar solvent re- veals that the lowest
    excited singlet state of 1 is (π,π*). The emission band
    peaking at 450 nm to 650 nm was the fluorescence of compound 1.
    No phosphorescence could be measured even in the low
    temperature matrix.The fluore- scence quantum yields of
    compound 1in cyclohexane, car- bon tetrachloride, benzene and
    methanol, with referring to anthracene, were 0.15, 0.02, 0.019
    and 0.0045, respective- ly. The lifetime of fluorescence of
    compound 1 was esti- mated as 9.8 ns by Stern-Volmer equation
    in assuming the diffusion-limit rate of triethylamine quenching
    study. The photoaddition of compound 1 with triethylamine
    proceeded in degassed benzene. The two major products were
    obtained in 8 hours' irradiation. One is a 1,2-pho- toaddition
    adduct, oxetane, 2, in 15% yield, and the o- ther is a
    1,4-photoaddition adduct, dioxene, 3, in 3% yield. The yield
    of compound 2 was raised to 35% in the presence of
    photosensitizer, benzophenone. Both of these two products may
    come from the second low excited triplet (n,π*) state of
    compound 1 in the analysis of the ab- sorption and emission
    spectrum as well as the quenching studies.
    The absorption spectrum of aceanthrenequinone,1, in non-polar

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