- 學位論文
異參茚并苯-苯乙烯寡聚物合成與性質之研究
The Synthesis and Properties of Isotruxene Derivatives Oligo(p-phenylene vinylene)s
摘要
本論文主旨在開發異參茚并苯之對苯乙烯寡聚物之合成，與光物理及電化學行為之探討，並期許能將其獨特的性質應用在有機異質介面塊材太陽能電池上。在合成部分，嘗試用鹼性較強的氫化鈉進行Horner-Wadsworth-Emmons 反應可以得到大部分為順式的對苯乙烯單元。再以不同長度的對苯乙烯單元與中心參異茚并苯進行Heck偶合反應得到ITr-OPV1、ITr-OPV2、ITr-OPV3、ITr-OPV4。在光物理行為中，因為中心骨架為異參茚并苯，具有獨特的鄰與對位共軛連結關係，ITr-OPVn均有較寬廣的吸收半高寬，且隨著共軛的延長有持續紅位移的現象。螢光光譜表現上，也有觀察到持續紅位移的現象，探討吸收光譜與螢光放射光譜紅位移程度與共軛電子對數目均有良好的線性關係，並發現其均有較高的螢光量子產率，較短的螢光生命期，所以放光速率均在7.0 × 108上下。 熱化學方面，ITr-OPVn展現較高的熱化學穩定性，有較高的裂解溫度及玻璃轉換溫度。電化學方面，ITr-OPVn在循環伏安法觀察到可逆氧化還原現象，並用式差脈衝伏安法測量其氧化電位，隨著共軛的對苯乙烯單元增長有下降的趨勢，顯示對苯乙烯單元有穩定ITr-OPVn氧化態電子的能力。
並列摘要
In this thesis, we report the synthesis of isotruxene-cored two-dimensional oligo(p-phenylene vinylene)s and explore their photophysical and electrochemical behavior. Their unique properties might be applied to organic electronics such as bulk heterojunction solar cells. In the synthetic part, we chose the base sodium hydride as a stronger base to carry out the Horner-Wadsworth-Emmons reaction so that we can get most trans oligo(p-phenylene vinylene)s as the major products. Moreover, we carried out the Heck coupling reaction with tribromoisotruxene and different length of arms to get the target compound ITr-OPV1, ITr-OPV2, ITr-OPV3 and ITr-OPV4. They display broad absorption bands due to the ortho-para conjunction in the isotruxene core. The number of conjugation electron pairs correlates to the extent of bathchromism in UV/vis absorption and fluorescence. We also discovered that they display high fluorescence quantum yield and short fluorescence lifetime, corresponding the fluorescence rate of 7.0 × 108 s-1. In thermochemical and electrochemical studies, ITr-OPVn display high decomposition temperatures and glass transition temperatures. The ITr-OPVn series are anodicallyreversible. We observe oxidation potential decreased along with the extention of conjugation length. The oligo(p-phenylene vinylene)s could help to stablize the oxidation state.
參考文獻
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