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国家自然科学基金(s50473062)

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分子间氢键对苯并菲柱状介晶性的影响:量子化学ONIOM(MO/MM)研究被引量:3
2007年
我们最近的实验显示:对于分子中含有酰胺基的苯并菲液晶化合物C18H6(OC5H11)3(OCH2CONHC4H9)3,对称化合物有比反对称异构体更高的清亮点和更有序的六方柱状介晶相,且与具有同样软链长度的分子中不含酰胺基的化合物C18H6(OC5H11)3(OCH2COOC4H9)3相比较,有更高的清亮点和更丰富的柱状介晶相.本文通过量子化学ONIOM(B3LYP/6-31G(d,p):UFF)计算,说明对于带酰胺基的分子,对称分子比反对称分子有较大的稳定化能和较高的转动势垒.对于对称性分子,带酰胺基的分子比带酯基的分子有较大的稳定化能和较高的转动势垒.这说明由酰胺基形成的分子间氢键起了稳定液晶相和锚定六方柱状相的作用,可以解释带酰胺基的分子和对称性分子有较高的清亮点和更有序的六方柱状介晶相.如果加长酰胺基的软链,则可使氢键锚定的扭转角减少,这样有利于提高电荷传输速率.
丁涪江赵可清
关键词:苯并菲盘状液晶分子间氢键
Synthesis of Mixed Tail Triphenylene Discotic Liquid Crystals: Molecular Symmetry and Oxygen-Atom Effect on the Stabilization of Columnar Mesophases被引量:7
2007年
Small change in chemical structure of discotic liquid crystals can cause big difference in their mesomorphism. Replacing of the alkoxy peripheral chains of triphenylene by oxygen-atom containing ester chains would result in novel mesomorphism. A series of mixed tail triphenylenes containing propoxyacetyloxy and alkoxy, abbreviated as C18H6(OCnH2n+1)3(OCOCH2OC3H7)3, n=4-8, and hexa(propyloxyacetyloxy)triphenylene, C18H6(OCOCH2OC3H7)6 were synthesized. Thermal gravimetry analysis (TGA) of three discogens showed that they had good thermal stability till 350 ℃. The mesomorphism was investigated through differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The preliminary X-ray diffraction (XRD) results of one compound showed that it exhibited ordered hexagonal columnar (Colho) mesophase. These mixed tail triphenylene derivatives possessed much stable Colho mesophase and wider mesophase ranges than their hexaalkoxytriphenylene C18H6(OR)6 and hexaalkanoyloxytriphenylene C18H6(OCOR')6 analogues. The asymmetrical compounds 2,6,11-trialkoxy-3,7,10-tri(2-propyloxyacetyloxy)triphenylenes with n=5-8 displayed higher clearing points and wider temperature ranges than their symmetrical isomers 2,6,10-trialkoxy-3,7,11-tri(2-propyloxyacetyloxy)- triphenylenes, while C18H6(OCOCH2OC3H7)6 had the highest clearing point due to the β-oxygen-atom effect.
赵可清胡平汪必琴余文浩陈红梅王新玲清水洋
关键词:TRIPHENYLENE
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