2017-01-012024-05-17https://scholars.lib.ntu.edu.tw/handle/123456789/681957摘要：有機共軛高分子已廣泛地應用於有機光電領域，其合成多以過渡金屬催化之偶合反應來聚合芳香環，因此製備有機金屬或其它主族元素試劑為必要之步驟，直接芳基化反應可直接活化碳－氫鍵並與親電性的芳香基鹵化物進行偶合反應，比傳統的過渡金屬偶合反應更為原子經濟且對環境更友善。本計劃著重於使用直接芳基化聚合反應來製備油溶性或水溶性的共軛高分子，以取代傳統的過渡金屬之聚合反應，項目可分為(1)改善氮雜環碳烯鈀金屬之催化系統；(2)改善直接芳基化聚合反應於合成共聚型共軛高分子的化學及位置選擇性；(3)發展氧化型的直接芳基化聚合反應；(4)發展水相之直接芳基化聚合反應；(5)發展不需過渡金屬之直接芳基化聚合反應。研究內容為一系列的反應優化步驟，從高分子PDI值的降低至提高反應的化學及位置選擇性至發展純碳－氫鍵的聚合反應至水相之聚合反應至不需過渡金屬之反應，以提供更優化的共軛分子聚合方法。另一方面，所合成之共軛高分子會鎖定在有機光電，如高分子太陽能電池及有機場效電晶體，有潛力的材料，並進一步驗證其光電表現。密度泛函理論及量子力學/分子力學亦會使用於計算聚合反應機制、化學鍵及性質分析，以建立理論解析與實驗及材料特性之關聯性。<br> Abstract: Organic conjugated polymers have been extensively used in organic optoelectronics. Preparation of conjugated polymers by conventional transition-metal catalyzed cross-coupling polymerization involves the use of organometallic or main-group reagents, which is synthetically tedious and environmentally unfriendly. Direct arylation provides a more atom-economical method, in which activation of C–H bond can be achieved without preparing organometallic or main-group reagents. This research proposal focuses on utilization of direct-arylation polymerization to synthesize organic conjugated polymers. The goals contain (1) improving the catalytic ability of N-heterocyclic carbene-based palladium catalysts, (2) increasing the chemo- and regio-selectivity of direct-arylation polymerization, (3) developing oxidative direct-arylation polymerization, (4) establishing aqueous direct-arylation polymerization, and (5) examining transition-metal free direct-arylation polymerization. A series of reaction optimizations will be performed with the aim of (1) achieving both low PDI values and high molecular weight, (2) enhancing the chemo- and regio-selectivity to afford highly stereo- and regio-regular polymers, (3) realizing C-H/C-H oxidative polymerization, (4) replacing organic solvents with water, and (5) establishing transition-metal free direct-arylation polymerization, aiming at providing more cost-effective and environmentally friendly synthetic methodology for conjugated polymers. On the other hand, even though this research proposal concentrates on investigating direct-arylation polymerization, it is not limited to methodology demonstration. Our target polymers are mainly promising materials in the field of polymer solar cells and organic field-effect transistors and their photovoltaic properties will be examined. Density functional theory will be carried out as well to calculate potential energy surface of the reactions, chemical bonding of the catalysts and intermediates, and physical properties of the polymers in order to look insight into the reaction mechanism and build the structure-properties relationship.