Hydrogen bonding liquid crystalline benzoic acids with alkylthio groups: phase transition behavior and insights into the cybotactic nematic phase

作者：Arakawa Yuki^*; Sasaki Yukito; Igawa Kazunobu; Tsuji Hideto

来源：New Journal of Chemistry, 2017, 41(14): 6514-6522.

DOI：10.1039/c7nj00282c

A simple but novel class of hydrogen bonding liquid crystalline benzoic acids with alkylthio (or alkylsulfanyl; SR) groups was established. In general, although it is difficult for laterally non-substituted rod-like molecules with an alkylthio group to form some mesophases, the present molecules exclusively form a nematic (N) regime, owing to spontaneous carboxylic dimerization. It was found that the number of carbons in the alkylthio groups strongly correlated with transition temperatures as well as nematogenic stability: odd-even effects. Even-members displayed wider monotropic and enantiotropic N phases, despite the fact that almost all odd-members showed either none or only monotropicnarrower ones. Interestingly, their thermal transition temperatures were lower compared to those for alkoxy (OR) analogues, on account of the small angle (or large bend) of the C-S-C bond as well as the low electron density on their aromatic ring due to the weak electron donor properties of alkylthio groups. Additionally, in-depth wide-angle X-ray diffraction measurements revealed that an alkylthio analogue exhibited significantly enhanced smectic clusters formed in the N regime (or Ncyb phase) as well as the cluster type close to smectic (Sm) A, in comparison with an alkoxy analogue exhibiting a clear SmC-type cluster. The results indicate that a robust S center dot center dot center dot S intermolecular interaction for an alkylthio group into a mesogen affects the kind of smectic cluster in the Ncyb phase.

• 出版日期2017-7-21