Polyynes with Aggregation-Induced Emission Characteristics: Synthesis and Their Photonic Properties

合成了三種含有四苯基乙烯結構的雙炔烴.這些雙炔烴單體通過在CuCl催化下在鄰二氯苯中進行的均聚反應可以高產率地生成線型聚炔.所得聚合物均可很好地溶解於常見有機溶劑中，並具有很高的熱穩定性.這類聚炔材料在溶液態時幾乎不發光，但在聚集態或者固態下可高度發光，表現出典型的聚集誘導發光性質.同時，這些聚合物具有高透光性，可以允許整個可見光區的光透過.其薄膜在400～1700 nm寬波長范圍內表現出高折射率（n=1.7787～1.6543）和低色差（D'=0.0003）.紫外光照射可誘使聚合物薄膜發生交聯過程，從而調控其折射率數值，並可生成高分辨率的熒光圖案.Tetraphenylethene-containing diacetylenes are synthesized and their homopolymerizations are catalyzed by CuCl in o-dichlorobenzene, furnishing linear polyynes in high isolated yields. All polymers possess good solubility in common organic solvents and enjoy high thermal stability. Whereas they are practically non-emissive when molecularly dissolved in good solvents, they become highly emissive when aggregated as nanoparticle suspensions in poor solvents or fabricated into thin films in the solid state, demonstrating a novel phenomenon of aggregation-induced emission. The polymers are highly transparent, allowing almost all light in the entire visible spectral region to transmit through. Thin films of the polymers show high refractive indices (n=1.7787~1.6543) in the wavelength region of 400~1700 nm and very low chromatic aberrations (D'=0.0003). Their n values can be modulated and their thin films can be crosslinked by UV irradiation, generating fluorescent patterns with high resolutions. © 2016 Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences.