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Why many luminescent liquid crystalline polymers (LLCPs) containing aggregation-induced emission luminogen (AIEgen) show weak emission is a question still to be answered. Herein, a series of LLCPs (α-Pns, n = 4, 8, and 12) with polynorbornene as main chain and two α-dicyanodistyrylbenzene (α-DCS) as side chain are successfully synthesized to solve this issue. Differential scanning calorimetry (DSC), polarized light microscopy (PLM), one-dimentional (1D), two-dimentional (2D) middle-angle and wide-angle X-ray scattering (MAXS and WAXS) results demonstrate that the polymers form smectic A (SmA) phase with the side chains interdigitated packed within the smectic layers. Meanwhile, the photophysical properties of α-Pns were investigated by ultraviolet–visible (UV–vis) absorption, steady state and time-resolved spectroscopy, and photothermal effect. Results show that the polymers are AIE active, but emit weak emission. The emission peak of α-Pns film red-shift from 473 to 531 nm, the quantum yield gradually increases from around 1.6% to 14.7%, and the photothermal conversion efficiency decreases from 39% to 19% with the alkyl tail length increased. The photothermal effect, but not photoluminescence, dominates the excited state relaxation.
This work was supported by the National Natural Science Foundation of China (NSFC) (Nos. 21875143, 21674065, and 21975215), the Innovation Research Foundation of Shenzhen (Nos. SGG20190222175202275, JCYJ20180507182229597, and JCYJ20180305125649693), and the Natural Science Foundation of Guangdong Province (No. 2016A030312002). Special thanks go to the Instrumental Analysis Center of Shenzhen University (Lihu Campus).