新型含共軛基團之[60]富勒烯亞甲基衍生物之合成鑑定與性質探討

Synthesis and Characterization of Conjugated Group-Bearing [60]Mathanofullerene Derivatives

黃子育(Tzu-Yu Huang)

指導教授 ： 芮祥鵬

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2010年)

摘要

[60]富勒烯亞甲基衍生物在高分子太陽能電池中扮演著一個良好的電子受體角色，其結構的不同會影響到分子本身的能階變化，進而影響太陽能電池的效率。在本篇研究中，我們合成一系列含有共軛噻吩官能基的C60衍生物，並
進一步探討其物理性質變化。
首先利用3-butoxy-3-oxopropanoic acid 與具有共軛噻吩官能基之醇類利用N,N’-dicyclohexylcarboidiimide (DCC)進行酯化反應，然後將產物與[60]富勒烯利用Bingel-Hirsch reaction 合成出具有不同thienyl官能基團的C60衍生物(n-butyl thien-2-ylmethyl)(1,2-methano[60]fullerene)-61,61 dicarboxylate (BTMMDC)、(n-butyl 2,2’-bithien-5-ylmethyl)(1,2-methano[60]fullerene)-61,61 dicarboxylate (BBTMDC)、 (n-butyl 2,2’;5’,2”-ter-5-thienylmethyl)(1,2-methano[60]fullerene)-61,61 dicarboxylate (BTTMDC)及(n-butyl(5-(7-(thien-2-yl)benzo[c][1,2,5]thiadiazol-4-yl)thien-2-yl)methyl)(1,2-methano[60]fullerene)-61,61dicarboxylate (BTBTMDC)
，並且透過核磁共振光譜儀(NMR)，基質輔雷射脫附質譜儀(matrix assisted laser desorption ionization-time of flight mass spectometry, MALDI-TOF MS)進行產物之結構鑑定，並且利用循環伏安法(cyclic voltammetry, CV)量測BTMDC、BBTMD
C、BTTMDC、BTBTMDC之lowest unoccupied molecular orbital (LUMO)能階，與ultraviolet-visible spectroscopy (UV-Vis)測量其UV吸收光譜變化。

關鍵字

[60]富勒烯亞甲基 ； Bingel-Hirsch reaction ； 噻吩寡聚物

並列摘要

[60]Mathanofullerene derivatives have been widely used as excellent electron acceptor in organic solar cells. It also has been demonstrated that the chemical structure of C60 adduts has profound effect on their optical properties and aggregation behavior, which are decisive factors affecting the power conversion efficiency of solar cells. In this research, a series of conjugated group-bearing methanofullerenes were designed, synthesized and well characterized.
Firstly, the esterfication of 3-butoxy-3-oxopropanoic acid and thienyl-based alco
hol were carried out using N,N’-dicyclohexylcarboidiimide (DCC). Then these moiety
es were bounded to C60 by the Bingel-Hirsch reaction to generate four [60]mathanoful
lerenes, including (n-butyl 2-thienylmethyl)(1,2-methano [60]fullerene)-61,61 dicarbo
-xylate (BTMDC), (n-butyl 2,2’-bithien-5-ylmethyl) (1,2-methano[60]fullerene)-61,6
1 dicarboxylate (BBTMDC), (n-butyl2,2’;5’,2”-terthien-5-ylmethyl)(1,2-methano[60]
fullerene)-61,61dicarboxylate(BTTMDC),(n-butyl(5-(7-(thien-2-yl)benzo[c][1,2,5]thiadiazol-4-yl)thien-2-yl)methyl)(1,2-methano[60]fullerene)-61,61 dicarboxylate (BTB
TMDC).
The molecular structure of these novel fullerene derivatives was characterized by 1H NMR, 13C NMR, and matrix-assisted laser desorption ionization- time of flight mass spectrometer (MALDI-TOF MS) techniques.Cyclic voltammetey (CV) was employed to determine their lowest unoccupied molecular orbital (LUMO) energy levels, and UV-Vis was utilized to estimate their optical bandgap.

並列關鍵字

[60]mathanofullerene ； Bingel-Hirsch reaction ； poly thiophene

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