One-pot three-component polymerization for in situ generation of AIE-active poly(tetraarylethene)s using Grignard reagents as building blocks

作者：Qiu, Zijie; Gao, Qingqing; Han, Ting; Liu, Xiaolin; Lam, Jacky W. Y.^*; Tang, Ben Zhong^*

来源：Polymer Chemistry, 2020, 11(35): 5601-5609.

DOI：10.1039/d0py00874e

• AGGREGATION-INDUCED EMISSION
• INTERNAL ALKYNES
• POLYMERS
• EFFICIENT
• STRATEGY
• ROUTE
• ACIDS

The development of efficient multi-component polymerizations from handy monomers to synthesize multifunctional polymers with complicated structures is an attractive but challenging research topic. In this work, a facile, one-pot, three-component polymerization route forin situgeneration of polymers with aggregation-induced emission (AIE) characteristics has been developed. Under the catalysis of NiCl2, polycoupling of dihaloarenes, internal diynes, and Grignard reagents proceeded efficiently, generating poly(tetraarylethene)s (PTAEs) with high number average molecular weights (M(n)up to 16 800) in high yields (up to 93%) in only three hours. The obtained PTAEs show typical AIE characteristics due to thein situ-generated AIEgen units, tetraphenylethene, in the polymer backbone. Utilizing the AIE property, aggregate-state PTAE could serve as an efficient fluorescent chemosensor for picric acid and Ru(3+)with amplified sensitivity, and the quenching constants reached 2.33 x 10(6)L mol(-1)and 6.85 x 10(4)L mol(-1), respectively. Furthermore, the polymer thin films showed modulable refractive indices under UV irradiation in the wide wavelength region of 400-900 nm, presenting great potential in optical fiber applications. Well-resolved 2D fluorescent patterns can also be generated by photo-oxidation of the thin films of PTAEs under UV irradiation through a copper photomask. This work provides another successful example of anin situgeneration strategy for functional AIE polymers, broadening the scope of the monomer library.

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