Robust Angular Anisotropy of Circularly Polarized Luminescence from a Single Twisted-Bipolar Polymeric Microsphere

in: Journal of the American Chemical Society (2021)
Oki, Osamu; Kulkarni, Chidambar; Yamagishi, Hiroshi; Meskers, Stefan C. J.; Lin, Zhan-Hong; Huang, Jer-Shing; Meijer, E. W.; Yamamoto, Yohei
It has long been surmised that the circular polarization of luminescence (CPL) emitted by a chiral molecule or a molecular assembly should vary with the direction in which the photon is emitted. Despite its potential utility, this anisotropic CPL has not yet been demonstrated at the level of single molecules or supramolecular assemblies. Here we show that conjugated polymers bearing chiral side chains self-assemble into solid microspheres with a twisted bipolar interior, which are formed via liquid−liquid phase separation and subsequent condensation into a cholesteric lyotropic liquid crystalline mesophase. The resultant microspheres, when dispersed in methanol, exhibit CPL with a glum value as high as 0.23. The microspheres are mechanically robust enough to be handled with a microneedle under ambient conditions, allowing comprehensive examination of the angular anisotropy of CPL. The single microsphere is found to exhibit distinct angularly anisotropic birefringence and CPL with glum up to ∼0.5 in the equatorial plane, which is 2.5-fold greater than that along the polar axis. Such optically anisotropic solid materials are important for the application to next-generation microlight-emitting and visualizing devices as well as for fundamental optics studies of chiral light−matter interaction.

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