Orientational order of guest molecules in aligned liquid crystal as measured by EPR and UV–vis techniques

Abstract

Orientational order of guest molecules in aligned liquid crystal 4-cyano-4′-pentylbiphenyl (5CB) is studied via optical dichroism and electron paramagnetic resonance (EPR) spectra measurements. The guest molecules used are bifunctional molecules bearing paramagnetic nitroxide group and photochromic azobenzene moiety. The bifunctional probe with rigidly bonded nitroxide and azobenzene moieties was found to align as a whole, while flexible long spacer between the moieties provides independent alignment for the nitroxide and azobenzene parts. Intermolecular interactions responsible for the alignment of azobenzene and nitroxide moieties of the probe molecules are discussed. The molecules with cis-configuration of azobenzene moiety are able to align in the liquid-crystalline medium, but to a lesser extent than the molecules with trans-configuration. Directions of orientational axes and characteristics of rotational mobility of spin probes are determined. Second, fourth and, in some cases, sixth rank order parameter values are found.

Keywords:

• aligned liquid crystal
• guest–host effect
• EPR spectra simulation
• spin probes
• orientation distribution function

Acknowledgements

The authors are grateful to Prof. S. Nakatsuji (University of Hyogo, Japan) for the provision of bifunctional probes and to Prof. G.K. Elyashevitch (Institute of Macromolecular Compounds, RAS, Russia) for the provision of stretched porous polyethylene.

The work was supported by Russian Foundation for Basic Research, grant No. 12-03-31114.