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吉林大学, 超分子结构与材料教育部重点实验室, 吉林, 长春, 130012
收稿日期:2004-08-26,
修回日期:2005-01-21,
纸质出版日期:2006-01-20
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李昱鹏, 何琳, 陆丹, 马於光, 李国文. MEH-CN-PPV中Z/E的构型[J]. 发光学报, 2006,27(1): 100-104
LI Yu-peng, HE Lin, LU Dan, MA Yu-guang, LI Guo-wen. Z/E Configuration in MEH-CN-PPV[J]. Chinese Journal of Luminescence, 2006,27(1): 100-104
用Knoevenagel方法
合成了MEH-CN-PPV
通过对其
1
H-核磁共振(
1
H-NMR)谱的研究
在MEH-CN-PPV的1H-NMR谱中发现烯键的Z/E两种构型的信号
通过积分面积初步估算E构型占15%
Z构型占85%。并且合成了模型化合物——齐聚物(E
E)-1
4-二(1-氰基-2-苯乙烯基)-2-(2-乙基己氧基)-5-甲氧基苯
其发生异构时
1
H-NMR谱的变化与MEH-CN-PPV的Z/E两种构型在1H-NMR谱中的信号吻合。
CN-PPV is one of the important series of PPV and its derivatives
demonstrating very high quantum efficiency of over 4% in a two-layers device
ITO/PPV/CN-PPV/Al. It is widely known that the defects in the polymer backbone can affect the properties of the device. The main structural defects in PPV-type conjugated polymers involve the "tetrahedral" structural segments and the E-double bone configurations. In order to achieve a better understanding to the structure of MEH-CN-PPV
the model compound (8a) (Z
Z-configuration) was synthesized. The Z/E-isomerization of the vinylene moiety with cyano group happened easily under the influence of visible and UV light. (8a) dissolved in chloroform was irradiated in daylight for 2 days under purging nitrogen. Its NMR spectrum become more complex
which showed the occurrence of the Z/E-isomerization. Through a careful separation for this mixture by column chromatography (silica gel
cyclohexane/ dichloromethane 2:5) in the dark
two new compounds (8b) (a green solid) and (8c) (yellow oil) were obtained. According to the
1
H-NMR spectra
the configuration of (8b) was E
E and that of (8c) was Z
E. In the
1
H-NMR spectrum of the copolymer MEH-CN-PPV
the main signals were similar to (8a)
which indicated that the configuration of the copolymer MEH-CN-PPV was mainly Z. Some feeble signals at 6.47×10
-6
and 3.32 ×10
-6
were similar to the signals of the protons on the vinylene bond and OCH related with the E-configuration in (8b) and (8c). Hence these signals can prove the presence of the E-configuration in MEH-CN-PPV backbone. The ratio between the signal (d) and the signal (a) was 0.09. The contents of the Z/E-configuration could be estimated: for Z-configration was 85% and 15% for E-configration.
Burroughes J H,Bradley D D C,Brown A R,et al.Light-emitting diodes based on conjugated polymers[J].Nature,1990,347:539-541.
Yuan Renkuan,Kong Fan,Ou Changgang,et al.Conformations and optical characteristics of MEH-PPV with different states[J].Chin.J.Lumin.(发光学报),2005,26(5):655-658 (in Chinese).
Greenham N C,Moratti S C,Bradley D D C,et al.Efficient light-emitting diodes based on polymers with high electron affinities[J].Nature,1993,365:628-630.
Moratti S C,Cervini R,Holmes A B,et al.High electron affinity polymers for LEDs[J].Synth.Met.,1995,71:2117-2120.
Lange F J,Leuze M,Hanack M.Z/E isomerization of poly-para-phenylenevinylene model compounds[J].J.Phys.Organ.Chem.,2001,14:474-480.
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