Red-Shifted Luminescence of Acrylonitrile-Containing Copolymers: A Matter of One Methyl Unit

作者：Li, Xinyu; Dai, Junhao; Zhang, Rui^*; Wen, Tao^*

来源：Macromolecular Rapid Communications, 2023.

DOI：10.1002/marc.202300666

• copolymer
• non-conventional luminescence
• polyacrylonitrile
• photophysics

Copolymerization provides an effective approach to tune the photophysical properties of non-conventional luminescent polymers (NCLPs). In this study, the controlling of intrinsic emissions of polyacrylonitrile (PAN) copolymers is revealed by a delicate difference of secondary monomers. The introduction of methacrylate comonomers can induce a 70-nm red-shifting in the PL emission of copolymers compared with that of acrylate-containing copolymers. The mechanism of such "copolymerization induced red-shifting" in PAN copolymers is investigated. It is demonstrated that the presence of the alpha-methyl group in the copolymers can enhance the chain rigidity and through-space conjugation (TSC) of C equivalent to N groups, resulting in the red-shifting of emission. @@@ The intrinsic luminescence of acrylonitrile-containing copolymers can be significantly tuned by the chemical structures of comonomers. The presence of alpha-methyl groups of methacrylate comonomers can lead to a 70-nm red-shifting on the photoluminescent emissions, compared to acrylate-containing copolymers, due to the enhanced chain rigidity and through-space conjugation (TSC).image