新型碳六十衍生物的合成與分析見鑑定

Synthesis and Characterization of (benzyl-n-alkyl)(1,2-methanofullerene C60)-61,61-dicarboxylate

蔡欣翰(Hsin-Han Tsai)

指導教授 ： 芮祥鵬 ； 王立義

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2008年)

摘要

本研究之主要目的在於合成一系列可用於太陽能電池且具有良好溶解性的
新型碳六十衍生物。首先，苯甲醇和meldrum acid在110~120 oC的環境下反應三
小時，合成出malonic mono ester。然後malonic mono ester分別與正丁醇、正己
醇、正辛醇與正十二碳醇在DCC及HOBT的存在下進行酯化反應，合成出
(benzyl-n-butyl) malonic ester, (benzyl-n-hexyl) malonic ester , (benzzyl-n-octyl)
malonic ester 和(benzyl-n-dodecyl) malonic ester。再將(benzyl-n-butyl) malonic
ester, (benzyl-n-hexyl) malonic ester , (benzyl-n-octyl) malonic ester 和(benzyl-ndodecyl)
malonic ester與碳六十在鹼性的環境下進行Bingel reaction，由於鹼性環
境下 malonic ester 被拔除氫後被鹵素取代，接著碳上的鹵素游離，而使 malonic
ester 上有了一對未鍵結的電子對，再去跟碳六十反應 ，得到產物(benzyl-nbutyl)(
1,2-methanofullerene C60)-61,61- dicarboxylate (BBMDC)
，(benzyl-n-hexyl) (1,2-methanofullerene C60)-61,61- dicarboxylate (BHMDC)，
(benzzyl-n-octyl) (1,2-methanofullerene C60)-61,61- dicarboxylate (BOMDC) 和
(benzyl-n-dodecyl) (1,2-methanofullerene C60)-61,61- dicarboxylate (BDMDC)。
再分別以H1 NMR、C13 NMR、UV-vis、MALDI-TOF MS及EA等儀器分析
鑑定其化學結構與組成。再以循環伏安法(cyclic voltammetry, CV)測出其LUMO
及以UV- vis測定材料能隙(band gap)並以AFM所觀察碳六十衍生物與P3HT摻混後之奈米形態。

關鍵字

碳六十(C60)衍生物 ； Bingel-Hirsch cyclopropanation ； 有機太陽能電池材料

並列摘要

Organic solar cells using the mixture of [6,6]-phenyl C61-butyric acid methyl
ester (PCBM) and poly(3-hexylthiophene) (P3HT) as photoactive material have
attract considerable interests in recent years because a power conversion efficiency
around 5 % has been demonstrated by carefully tuning the fabrication process. In this
study, a serious of C60 derivatives, (benzyl-n-butyl)(1,2-methanofullerene C60)-61,61-
dicarboxylate (BBMDC), (benzyl-n-hexyl) (1,2-methanofullerene C60)-61,61-
dicarboxylate (BHMDC), (benzzyl-n-octyl) (1,2-methanofullerene C60)-61,61-
dicarboxylate (BOMDC) and (benzyl-n-dodecyl) (1,2-methanofullerene C60)-61,61-
dicarboxylate (BDMDC), were synthesized by the Bingel cyclopropanation of
malonic ester-bearing molecules and C60 cage. The products were characterized using
1H NMR, 13C NMR, UV-vis, EA, MALDI TOF-MS and cyclic voltammetry (CV)
techniques. The new C60 derivatives possess much better solubility than PCBM in
many organic solvents such as dichloromethane, toluene, chlorobenzene and odichlorobenzene
(o-DCB), allowing the use of higher concentration of P3HT and C60
derivative in the cell fabrication process. Moreover, the morphology of the
photoactive blend of P3HT and these new C60 derivatives were examined by atomic
force microscopy AFM.

並列關鍵字

Fullerene (C60) derivatives ； Bingel-Hirsch cyclopropanation ； Organic Photovoltaic Solar Cell Material

參考文獻

Buckminsterfullerene". Nature 1985, 318, 162.

Nature 1990, 347, 354.

3. W. A. Scrivens, P. V. Bedworth, and J. M. Tour. J. Am. Chem. Soc. 1992, 114,

4. C. Bingel, Chem. Ber. 1993, 126, 1957.

8. E. W. Godly and R. Taylor. Pure Appl. Chem. 1997, 69, 1411.