We synthesized disubstituted liquid crystalline polyacetylene (diLCPA) derivatives bearing 4-nonyloxy phenyl groups with lyotropic and thermotropic LC behavior. The poly(diphenylacetylene) main chain structure of the diLCPAs and the chirality induced with either chiral moieties or chiral dopants allow the formation of a highly ordered lyotropic N*-LC phase. Circular dichroism (CD) spectra of the diLCPAs imply that one-handed intrachain helical structures are formed in solution, while interchain helical π-stacking between the polymer main chains are formed in cast film and in the N*-LC state. Absorption dissymmetry factors (g(abs)) in the N*-LC state show values on the order of 10(-1). The N*-LC state facilitates the formation of helically π-stacked structures with a high degree of helical ordering of the diLCPA and is indispensable for the generation of circularly polarized luminescence (CPL) with high emission dissymmetry factors (g(em)) on the order of 10(-1). To the best of our knowledge, this is the highest reported value of CPL achieved for aliphatic, conjugated polymers. As an alternative to the thermotropic N*-LC phase, we have found that the lyotropic N*-LC phase of diLCPA could be promising materials possessing CPL functionality for use in next-generation π-conjugated organic optoelectronic devices, displays, and sensors.

An optically resolvable and thermally chiral‐switchable device for circularly polarized luminescence (CPL) is first constructed using a light‐emitting conjugated polymer film and a double‐layered chiral nematic liquid crystal (N*‐LC) cell. The double‐layered N*‐LC cell with opposite handedness at each layer is fabricated by adding each of two types of N*‐LCs into each of the cells, and the N*‐LCs consist of nematic LCs and chiral dopants with opposite chirality and different mole concentrations. The selective reflection band due to the N*‐LC is thermally shifted so that the band wavelength is close to the luminescence band of the racemic conjugated polymer, such as disubstituted polyacetylene (diPA), yielding CPL with opposite handedness and high dissymmetry factor values (|glum|) of 1.1–1.6 at low and high temperatures. The double‐layered N*‐LC cell bearing the temperature‐controlled selective reflection is useful for generating CPLs from racemic fluorescent materials and for allowing thermal chirality‐switching in CPLs, which present new possibilities for optoelectronic and photochemical applications.

We synthesized disubstituted liquid crystalline polyacetylene (di-LCPA) derivatives by polymerizing acetylene derivatives consisting of LC moieties either directly or indirectly attached to the main chain through flexible alkyl spacers. The di-LCPA derivatives show either enantiotropically thermotropic LC or lyotropic LC behavior. The origin of emission of substituted PAs, with respect to their substituents and structure, was elucidated. Depending on the substituents of the side chains, the polymers exhibit blue (470–485 nm) and green (500–540 nm) photoluminescence (PL) in chloroform and in cast film. The di-LCPA derivatives were macroscopically aligned using rubbing technique, and the aligned structures of the polymers are characterized in terms of main chain and side chain type alignments through XRD measurements. The emission color and alignment direction toward an external force in the di-LCPA derivatives are crucially determined by both the linkage forms (direct or indirect attachment) between the main chain and side chains and the molecular moieties (alkyl or aromatic moiety) of the side chains. The macroscopically aligned films of the polymers exhibit linearly polarized photoluminescence (LPL) with notable dichroic ratios. We fabricate multilayer electroluminescence (EL) devices using the polymers as the emissive polymer layer that emit 480 nm light with promising EL properties. We emphasize that although substituted PA derivatives are usually nonluminescent, the di-LCPA derivatives emit intense fluorescence with notable linear dichroism, and they could be promising for optically anisotropic luminescent materials.