鋸齒形與角形雙烷基雙噻吩稠四苯：設計、合成、性質鑑定以及應用於有機太陽能電池與有機場效電晶體

Abstract

本研究成功合成出兩種不同構型的雙噻吩稠四苯異構物，分別為鋸齒形的 chrysenedithiophene ( CDT ) 與角形的 tetracenedithiophene ( TDT )。所建立的合成包括三個重要步驟：第一三氟甲烷磺酸基比起溴基有更強的活性，優先進行 Sonogashira 耦合反應，得到雙炔基雙溴基萘；接下來溴基進行 Stille耦合反應得到雙炔基雙噻吩萘；最後化合物 ( CDT ) 是經由高溫鹼性的環境下進行 6 – π環化反應合成出中心為鋸齒形 chrysene 的 CDT ; 而化合物 ( TDT ) 是經由鉑金屬催化下進行 6 – π環化反應合成出中心為直線型 tetracene 的 TDT。在化合物 CDT 的部分，利用鈀金屬催化的Stille 耦合聚合與四種不同的電子受體 DTFBT、DTC8FBT、DTC8C12FBT與DPP 得到四種共軛高分子 PCDTFBT、PCDTDTC8FBT、PCDTDTC8C12FBT 與 PCDTDPP。在有機太陽能電池元件的表現中，PCDTDTC8FBT 有最高的Jsc 與 Voc 而有最高的光電轉換效率 ( PCE = 2% ) 。在有機場效電晶體元件方面，PCDTFBT 有較好的共軛主鏈平面性且電子受體部分沒有絕緣側鏈，因此有比較好的載子通道，而有不錯的電洞遷移率 (1.12 × 10-2 cm2V-1s-1) 。在化合物 TDT 的部分，發現了TDT 在溶液態有光照二聚化的性質，而且依光譜結果可推測得到的是單一異構物的二聚體。在得到的 TDT 單晶結構中， TDT 的晶體排列為頭對頭的π 面對 π 面的排列。並且利用再結晶後得到擁有比較好排列的 TDT 拿去做光照二聚反應，發現二聚反應的速率加快很多，由此現象推測得到的單一異構物二聚體為頭對頭的構型。

We successfully synthesize two different configuration of Zigage-shape chrysenedithiophene (CDT) and angular-shape tetracenedithiophene (TDT). The established synthetic procedure involves three important steps; First, the chemoselective Sonogashira coupling reaction on the trifluoromethanesulfonyloxy site over the bromine site enable selective formation of dialkyne-dibromonaphthene; then, the Stille coupling reaction on the bromine site enable formation of dialkyne-dithiophenenaphthene; finally, in the chrysenedithiophene part with base catalyst to undergo double 6π-cyclization to structure the central chrysene; in the teteracenedithiophene with platinum catalyst to undergo double 6π-cyclization structure the central tetracene core. The shape of the molecules plays an important role in determining the chemical properties of the compounds. The zigzag-shape CDT had lower HOMO and good chemical stability than the central linear-shape TDT. The 2,9-distannylate CDT –based monomer was copolymerized with fluorinated benzothiadiazole (FBT), two alkylated dithieny fluorinated benzothiadiazole (DTC8FBT and DTC8C12FBT) and ditheniodiketopyrrolopyrrole (DPP) unit, to furnish an alternating donor−acceptor copolymer poly(chrysenedithiophen-5,6-difluorobenzothiadiazole) (PCDTFBT), poly (chrysenedithiophen -4,7- octyldithieny -5,6- difluorobenzothiadiazole) (PCDTDTC8FBT), poly(chrysenedithiophen-4,7-octyldodecyldithieny-5,6-difluoro benzothiadiazole) (PCDTDTC8C12FBT) and poly(chryseneithiophene- dithienyldiketopyrrolopyrrole) (PCDTDPP). The photovoltaic device based on the PCDTDTC8FBT have the best power conversion efficiency (PCE = 2%) because it have high Voc and good Jsc than others. PCDTFBT achieved high of the thin-film-based field-effect transistors (FET) of mobility = 1.12 x 10-2 cm2 V−1 s−1 with an on−off ratio of 8 × 107 because of its good packing. In the TDT part we found that the TDT monomer in solution state treat with light, the central tetracene part would undergo photo-induced dimerization. We also found that we could get just one configuration of TDT dimer. TDT have head to head thiophene in same side packing. After recrystallization, TDT photo-dimerization become more quickly than without recrystallization. As the result, we conjecture that the TDT dimer we get was head to head and just one configuration.