title: Efficient and Regioselectivity-Tunable Metal-Free Polycycloaddition of Activated Azide and Alkynes.
abstract: The transition-metal catalyzed and metal-free click polymerizations have been developed as powerful tools for the construction of functional polymers with linear and hyperbranched structures. The latter provides a thorough solution for the completely removing metallic residues from the products encountered in the former. Compared to the activated alkyne-azide metal-free click polymerization, the activated azide-alkyne one is rarely studied. In this Communication, a perfluorophenyl-activated azide of hexane-1,6-diyl-bis(4-azido-2,3,5,6-tetrafluorobenzoate) is rationally designed and facilely prepared. Through systematical optimization of the reaction conditions, an efficient metal-free perfluorophenylazide-alkyne polycycloaddition is established, and polytriazoles with high molecular weights (up to 166 000) and excellent solubility are obtained in excellent yields (up to 93%) under mild reaction conditions. Interestingly, the regioselectivity of the reaction could be fine-tuned by the solvents and diyne monomers. Therefore, this work provides not only a powerful tool for the preparation of functional polytriazoles, but also an attractive method for fine-tuning their regioregularity.
authors.affiliation: State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, China.
authors.forename: Yongwei
authors.initials: Y
authors.lastname: Wu
authors.affiliation: State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, China.
authors.forename: Benzhao
authors.initials: B
authors.lastname: He
authors.affiliation: State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, China.
authors.forename: Jia
authors.initials: J
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, China.
authors.forename: Rongrong
authors.initials: R
authors.lastname: Hu
authors.affiliation: State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, China.
authors.forename: Zujin
authors.initials: Z
authors.lastname: Zhao
authors.affiliation: State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, China.
authors.forename: Fei
authors.initials: F
authors.lastname: Huang
authors.affiliation: State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, China.
authors.forename: Anjun
authors.initials: A
authors.lastname: Qin
authors.affiliation: State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, China.|Department of Chemistry, The Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong.
authors.forename: Ben Zhong
authors.initials: BZ
authors.lastname: Tang
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D001386:Azides / Q000737:chemistry*; D057930:Click Chemistry; D061565:Cycloaddition Reaction; D015394:Molecular Structure; D058105:Polymerization; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D014230:Triazoles / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000480:Alkynes; D001386:Azides; D011108:Polymers; D014230:Triazoles
keywords: activated azide; metal-free polycycloaddition; polytriazole; solvent-free; tunable regioselectivity