Remote-Controllable Molecular Knob in the Mesomorphic Helical Superstructures

A programed light-responsive chiral liquid crystal (LC) containing four photochromic azobenzene moieties covalently connected to a central bicyclic chiral core (abbreviated as AZ₄ICD) is newly designed, precisely synthesized, and efficiently applied as a remote-controllable molecular knob for the optically tunable thin film. First of all, phase evolutions and ordered structures of AZ₄ICD are systematically investigated by a combination of thermal, microscopic, scattering, and simulation techniques. Wide-angle X-ray diffractions of oriented AZ₄ICD samples indicate that the AZ₄ICD molecule itself basically forms layer structures: one is a low-ordered chiral smectic A LC phase (SmA*) with 5.61 nm layer periodicity at high temperatures, and two highly ordered smectic crystal (SmCr₁ and SmCr₂) phases are subsequently formed at lower temperatures with the anticlinically tilted molecular packing structures. The helical superstructures of chiral nematic LC phase (N*) can be spontaneously constructed by doping AZ₄ICD chiral agents into the achiral nematic molecules. Due to the bent conformational geometry of AZ₄ICD, the thermal window of blue LC phase (BP) is expanded by stabilizing the double twisted cylindrical building blocks. Remote-controllable phase transformations in the mesomorphic helical superstructures are demonstrated by tuning the wavelength of light.