第I部分 新穎單核鎳金屬觸媒之開發及其聚合反應研究 本研究中合成出一系列含有不同取代基的新穎中性鎳金屬觸媒。於此研究中以改性甲基氧化鋁(MMAO)做為聚合反應之共觸媒，並於不同的反應溫度下針對觸媒(1)~(5)做探討。我們發現各觸媒於100℃時可得到較高之活性，其中觸媒(2)的活性凌駕於其他觸媒之上，可達3.84 x 106 g (mol Ni h)-1。根據觸媒(2)、(1)、(5)的聚合反應數據顯示，活性的優劣為(2) > (1) > (5)，由此可推論於pyrrolylaldiminate主體的5號位置接上取代基能有效提升觸媒的活性。 第II部分 新穎有機薄膜電晶體材料DPDTT之開發 我們已經開發出2,6-di(phenylcarbonyl)dithieno[3,2-b:2A,3A-d] -thiophene (DPDTT)，目前已測量出DPDTT具有P型有機半導體材料之特性，其載子移動率可達1 x 10-2 cm2 V-1 s-1。藉由X光單晶繞射的解析，發覺DPDTT為一不共平面分子，因此其分子間堆疊並不理想，使得載子移動率不如預期。DPDTT需由真空蒸鍍的方法來製作元件，此一部分，由西北大學Tobin J. Marks實驗室協助製作及量測。而目前這DPDTT的元件製備條件仍在嘗試階段，希望能找出最適合的製程條件，以利未來對此類分子的材料做更多的結構改良，以期提昇其載子移動率並製作出元件效能更佳的有機薄膜電晶體。 Part I. New Neutral Nickel(II) Catalysts Syntheses and Their Norbornene Polymerization Studies A series of new neutral nickel(II) catalysts with different substituents [(1)~(5)] have been synthesized. Catalysts (1)~(5) for the vinylic polymerization of norbornene have been investigated, using modified methylaluminoxane (MMAO) as a cocatalyst. Different polymerization temperatures have been studied and all of the five catalysts have shown higher activities at 100℃, whereas catalyst (2) demonstrated the highest activity [3.84 x 106 g (mol Ni h)-1]. The ordering of activities, ranking as (2) > (1) > (5), reveal that bulky substituents at the 5-position of pyrrolylaldiminate ligand can promote activity effectively. Part II. New DPDTT for Organic Thin Film Transistor 2,6-di-(phenylcarbonyl)-dithieno[3,2-b:2A,3A-d]thiophene (DPDTT) has been synthesized and exhibited as P-type semiconductor with 1 x 10-2 cm2 V-1 s-1 mobility. The molecular structure of DPDTT has been determined by single-crystal X-ray diffraction and reveals that DPDTT is not a coplanar molecular, leading to a not very high mobility. The DPDTT device fabrication is assisted by Tobin J. Marks group at Northwestern University via vacuum deposition. The optimum condition of the device fabrication for DPDTT and new material are currently in process. Hopefully, new DTT derivatives with better mobility and easier fabrication will be obtained in the future.
