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Living Crystallization-Driven Self-Assembly of Oligo(p-phenylene vinylene)-Containing Block Copolymers: Impact of Branched Structure of Alkyl Side Chain of π-Conjugated Segment

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Abstract

The structure of side chains of π-conjugated segments is a critical factor determining living crystallization-driven self-assembly (CDSA), a versatile platform to generate fiber-like nanostructures with precise length and composition. Herein, we design and synthesize three block copolymers (BCPs) containing same corona-forming poly(N-isopropyl acrylamide) (PNIPAM) segment, but different core-forming π-conjugated oligo(p-phenylene vinylene) (OPV) with linear pentyl (l-OPV), racemic 2-methyl butyl (r-OPV) and stereo-regular chiral (S)-2-methyl butyl (c-OPV) side chains, respectively. By using these BCPs of l-OPV-b-PNIPAM47, r-OPV-b-PNIPAM47 and c-OPV-b-PNIPAM47 as model, we aim to get a deep insight into how steric and stereo-regular effect induced by branched alkyl side chains of OPV segment affects the living CDSA. The results showed that l-OPV-b-PNIPAM47 exhibits typical characteristics of self-seeding and seeded growth of living CDSA to give uniform fiber-like micelles of controlled length. On the contrary, r-OPV-b-PNIPAM47 and c-OPV-b-PNIPAM47 with branched racemic and stereo-regular chiral alkyl side chains are more prone to self-nucleation during the micellar elongation to give short and polydisperse fiber-like micelles. The obvious self-nucleation during the micellar elongation of r-OPV-b-PNIPAM47 and c-OPV-b-PNIPAM47 is due to the increase of steric repulsion with OPV units induced by branched alkyl side chains, not the stereo-irregular effect of racemic alkyl side chains.

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Acknowledgments

This work was financially supported by National Science Foundation for Distinguished Young Scholars (No. 51825304), the National Natural Science Foundation of China (Nos. 52122314, U22A20131, 51873229 and 51961145103), the Youth Innovation Promotion Association of CAS (No. Y2020062), Shanghai Scientific and Technological Innovation Project (Nos. 20JC1415400, 21520780100, 22JC1401000 and 22ZR1475400), Innovation Program of Shanghai Municipal Education Commission (No. 2019-01-07-00-05-E00012) and East China University of Science and Technology (No. SLD13223004). The authors thank Dr. Kun Cui for his assistance in TEM measurements and the beamline BL16B1 at SSRF for providing the beam time.

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Authors and Affiliations

  1. School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai, 200093, China

    Yang Song & Chun Feng

  2. Shanghai Key Laboratory of Advanced Polymeric Materials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China

    Chun Feng

  3. Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, 200032, China

    Yang Song, Bo **ang, **ao-Yu Huang, Guo-Lin Lu & Chun Feng

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Correspondence to **ao-Yu Huang or Chun Feng.

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Living Crystallization-Driven Self-Assembly of Oligo(p-phenylene vinylene)-Containing Block Copolymers: Impact of Branched Structure of Alkyl Side Chain of π-Conjugated Segment

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Song, Y., **ang, B., Huang, XY. et al. Living Crystallization-Driven Self-Assembly of Oligo(p-phenylene vinylene)-Containing Block Copolymers: Impact of Branched Structure of Alkyl Side Chain of π-Conjugated Segment. Chin J Polym Sci 41, 574–584 (2023). https://doi.org/10.1007/s10118-023-2893-7

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