Cascade Polyannulation of Diyne and Benzoylacetonitrile: A New Strategy for Synthesizing Functional Substituted Poly(naphthopyran)s

详细信息    查看全文

• 作者：Yajing Liu ; Zheng Zhao ; Jacky W. Y. Lam ; Yueyue Zhao ; Yuncong Chen ; Yong Liu ; Ben Zhong Tang
• 刊名：Macromolecules
• 出版年：2015
• 出版时间：July 14, 2015
• 年：2015
• 卷：48
• 期：13
• 页码：4241-4249
• 全文大小：527K
• ISSN：1520-5835

文摘

A new strategy for synthesizing multisubstituted poly(naphthopyran)s (PNPs) with novel functionalities was described. The cascade oxidative polyannulation of benzoylacetonitrile and internal diynes are catalyzed by [RhCp*Cl₂]₂ and Cu(II) acetate in dimethylformamide at 90 掳C, generating PNPs with high molecular weight of up to 19 300 in excellent yields (isolation yield up to 96.4%). This polymerization method enjoys the remarkable advantages of high reaction rate, high efficiency, and atom-economy. All of the polymers show good solubility in common organic solvents and high thermal stability (degradation temperature up to 431 掳C). The thin films of PNPs display high refractive indices (1.5137鈥?.7524) in a wide wavelength range of 450鈥?600 nm. PNP containing tetraphenylethene units can be utilized to generate a well-resolved nanoscale photopattern by UV irradiation of its film through a copper mask. The PNPs exhibit the phenomena of mechanochromism and vapochromism: their emission is turned on upon scratching and solvent fuming their solid powders. Such attributes allow the polymers to be used as security materials or fluorescent indicators in various fields.