Cholesteric Liquid Crystalline Polyether with Broad Tunable Circularly Polarized Luminescence.

Strong circularly polarized luminescence (CPL) with high purity and broad tunability was achieved in a new type of polyether-based cholesteric liquid crystalline (CLC) copolymers comprising chiral cholesteryl, nematic mesogens, and cross-linkable moieties. The phase boundary diagram of the copolymers was constructed, wherein the CLC phase in a wide composition and temperature window down to room temperature was achieved. Furthermore, reflection colors across the infrared and visible light regions can be continuously tuned by altering composition or temperature, which can be further fixed in the flexible CLC elastomer by photo-cross-linking. Introducing achiral dyes in the CLC thin films can generate strong CPL with distinct handedness and high dissymmetry factors (glum). Particularly, the left-handed full-color CPL is obtained by selective circularly polarized scattering in the spectral region outside the band gap of the CLC thin film, and the right-handed CPL with glum up to -1.05 is achieved within the band gap of the CLC thin film following the selective circularly polarized reflection mechanism. This type of CPL active material is expected to have potential applications in liquid crystal display and photonics.

Chiral Photonic Liquid Crystalline Polyethers with Widely Tunable Helical Superstructures.

Liquid crystalline polymers with tunable structures on the scale of visible wavelength are important in optical technology due to their enhanced mechanical stability, processability, and structural integrity. Herein, we report a series of cholesteric liquid crystalline (CLC) polyethers with a widely tunable pitch length and a broad CLC phase window through a bottom-up structural design. The well-defined multicomponent polyethers were successfully synthesized by utilizing monomer-activated anionic ring-opening polymerization. Through adjustment of the composition of chiral cholesteryl (Ch) and photochromic azobenzene (Az) mesogenic moieties, rich phase behaviors have been discovered, and a phase boundary diagram was constructed consequently, wherein cholesteric helical superstructures in a broad composition range and temperature window straight down to the glassy state at room temperature were achieved. Particularly, the planar oriented helical superstructures can exhibit widely tunable and switchable reflections over the entire visible range across red, green, and blue colors through temperature and light control, which are closely related to the extraordinary flexibility of the polyether backbone. Their thermo-light dual-responsive properties provide an alternative opportunity to fabricate smart and switchable polymeric LC materials for optical applications.

Quasi-Living Copolymerization of Aryl Isocyanates and Epoxides.

Nontraditional polyurethane (PU) has been successfully synthesized by anionic copolymerization of some typical aryl isocyanates and epoxides with ammonium halide onium salt (Lewis base) as the initiator and triisobutylaluminum (Lewis acid) as the activator and the synergistic coordinator. In contrast to the traditional step-growth approach, this chain-growth copolymerization can maintain the anionic propagation site and exhibit some living features with a high activity, by which the copolymers synthesized have narrow molecular weight distributions and discrete end groups. The copolymer is primarily constituted by a urethane linkage, and the byproducts of isocyanurate trimer and oxazolidinone can be effectively suppressed as the polymerization proceeds. Density functional theory (DFT) calculations were also performed to support the proposed reaction mechanism.