ABSTRACT
Novel cinnamic-acid-derived H-bonded liquid crystals with enantiotropic BP*s were facilely prepared. When simply modifying the donor-acceptor ratio, the proportion of (S)-4-(2-octanyloxy) cinnamic acid to 4-(4-propylcyclohexyl) phenyl isonicotinate, the generated BP temperature ranges were consequentially extended with the widest range of about 10 °C, which is seldom found in enantiotropic BP materials. The optimized results of density-functional-theory calculations show that cinnamic-acid-derived mesogens have a bent shape and thus could be beneficial to stabilize enantiotropic blue phases.
ABSTRACT
Density functional (B3LYP) calculations using the 6-31++g basis set have been employed to study the title reaction between the cationic 1,3-dipolar 1-aza-2-azoniaallene ion (H2C=N(+)=NH) and ethene. Our calculations confirmed that [3 + 2] cycloaddition reaction takes place via a three-membered ring intermediate. In addition, solvent effects and substituent effects were also studied. For the reactions involving tetrachloroethene, there are two attacking sites. One is on the NH group in the 1-aza-2-azoniaallene ion, another is on its terminal CH2 group, and they are competitive for both approaching positions. Electron-releasing methyl substituents on ethene favor the reaction, and the potential energy surface is quite different from the previous one.
