Controlled Synthesis of Cyclic‐Helical Polymers with Circularly Polarized Luminescence

Xu, Lei; Gao, Bao-Rui; Xu, Xun-Hui; Zhou, Li; Liu, Na; Wu, Zong‐Quan

doi:10.1002/ange.202204966

Cited by 7 publications

(6 citation statements)

References 57 publications

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“…Experiments have established that the difference in backbone topology results in different molecular properties, e.g., cyclic BBPs exhibit a more compact shape and less interchain association , than their linear analogues. Although experiments ,− and dissipative particle dynamics simulations have elucidated many macroscopic properties of cyclic BBPs such as viscosity and self-assembled structures, the molecular-level details of structure and dynamics are still missing. Obviously, it would be informative to investigate the similarities and differences in the conformational behavior and properties of cyclic and linear BBPs in order to achieve a fundamental understanding of the chain topology effect.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, cyclic BBPs have emerged as a very interesting material. Experiments have established that the difference in backbone topology results in different molecular properties, e.g., cyclic BBPs exhibit a more compact shape and less interchain association , than their linear analogues. Although experiments ,− and dissipative particle dynamics simulations have elucidated many macroscopic properties of cyclic BBPs such as viscosity and self-assembled structures, the molecular-level details of structure and dynamics are still missing.…”

Section: Introductionmentioning

confidence: 99%

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Cyclic vs Linear Bottlebrush Polymers in Solution: Side-Chain Length Effect

Chen

Dormidontova

2023

Macromolecules

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Bottlebrush polymers (BBPs) of different architecture are of considerable interest for a broad range of applications, including nanomedicine, electronics, and self-healing materials. Using atomistic molecular dynamics simulations, we investigate and compare the structural and hydration properties of cyclic and linear poly(vinyl alcohol)-graft-poly(ethylene oxide) (PVA-g-PEO N sc ) BBPs in aqueous solution as functions of PEO side-chain length, N sc. We find that overall cyclic BBPs are smaller than the corresponding linear BBPs and their shape changes from donutlike to disklike to starlike with increasing side-chain length, while linear BBPs vary in shape from an expanded coil to a rod/cylinder. The radius of gyration of cyclic BBPs increases with an increase of the side-chain length at a somewhat slower rate than the linear BBPs but follows the same scaling R g ∼ N sc 0.58 in the limit of long side chains. For short grafts, we determine that the persistence length, l p, for both cyclic and linear BBPs increases in a similar manner following an l p ∼ N sc 0.54 dependence. In the long side-chain limit, the persistence length (l p) of cyclic BBP saturates, while for linear BBPs l p strongly increases following the expected scaling relation l p ∼ N sc 15/8. We propose a scaling model that shows that the fraction of side-chains located inside the cyclic BBPs depends on the radius of the backbone ring and significantly decreases with an increase of graft length. For both cyclic and linear BBPs, the hydrogen bonding between PEO side chains and water is somewhat reduced near the backbone, where local chain stretching is observed, while reaching full hydration on the periphery. Overall, the hydration shell within 1 nm of the cyclic BBP backbone is found to be more dynamically stable compared to linear BBPs.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Cyclic vs Linear Bottlebrush Polymers in Solution: Side-Chain Length Effect

Chen

Dormidontova

2023

Macromolecules

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“…The helix is an essential secondary structure in biomacromolecules and ubiquitous in nature, − playing an important role in living systems. Inspired by nature, scientists, especially chemists, have designed and prepared various helical polymers. − Among them, helical poly(phenyl isocyanide)s (PPIs) exhibit a stable helical structure and have attracted great attention because of their wide applications in chiral separation, chiral recognition, asymmetric catalysis, etc. − PPIs are commonly prepared using Ni(II), Rh(III), or Pd(II) complexes. − Among them, Pd(II) complexes are air-stable and highly active. Because the Pd(0)/ t -Bu 3 P system can initiate the polymerization of relevant fluorine monomers to afford Pd(II)-terminated PF, this Pd(II)-containing PF could be expected to serve as a catalyst for the polymerization of phenyl isocyanide monomers, rendering functional PF- b -PPI copolymers, exhibiting distinctive optical properties and self-assembly behavior.…”

Section: Introductionmentioning

confidence: 99%

Polyfluorene-block-poly(phenyl isocyanide) Copolymers: One-Pot Synthesis, Helical Assembly, and Circularly Polarized Luminescence

et al. 2023

Self Cite

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Optically active π-conjugated block copolymers are of considerable significance and interest, but their controlled synthesis and helical self-assembly remain challenging. In this study, π-conjugated block copolymers consisting of polyfluorene (PF) and poly(phenyl isocyanide) (PPI) segments were facilely prepared in one pot through two sequential polymerizations. First, a Pd(II)terminated PF precursor was synthesized via the Suzuki cross-coupling polymerization of 7-bromo-9,9-dihexylfluorene-2-boronic acid pinacol ester, which was catalyzed using a Pd(0)/t-Bu 3 P system. Then, PF-b-PPI copolymers with controlled molar mass and narrow dispersities were fabricated via controlled polymerization of phenyl isocyanide monomers utilizing Pd(II)terminated PF as the catalyst. Benefiting from the π-conjugated structure of the PF block and the helicity of the PPI block, the resulting PF-b-PPI copolymers could self-assemble into single-handed helical nanofibers. In the self-assembly process, chirality was transferred from the helical PPI block to the self-assembled helical nanofibers, thereby endowing them with optical activity and excellent circularly polarized luminescence properties.

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“…Poly(phenyl isocyanide) (PPI) is a main chain helical polymer that forms a helical structure. , Side chain modification is facile because various reactions can be applied to the phenyl group. , In this regard, studies using PPI derivatives have been reported in the research field of artificial helical polymers. − PPI offers a wide range of reaction designs, enabling the creation of a wide range of functional materials. The helical structure provided by PPI can be a label for block copolymers. − The introduction of a sufficiently long substituent is a flexible substituent to the PPI π-framework, effectively inducting the liquid crystal nature of PPI. Furthermore, the introduction of chiral units into the side chains can provide chiral monomer precursors.…”

Section: Introductionmentioning

confidence: 99%

Self-Inductive Asymmetric Synthesis of Polyisocyanides in Liquid Crystal

et al. 2023

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Monomers grow by leaps and bounds in their enhanced environment. This study presents the synthesis of optically active polyisocyanides in a cholesteric liquid crystal (CLC) reaction field induced by itself and evaluates the liquid crystallinity of the resultant polymer and the magnetic orientation. Polymerization of a chiral isocyanide monomer in a chiral liquid crystal reaction field was performed. The chiral liquid crystal reaction field showing a fingerprint-like image under polarizing optical microscopy observations was prepared by adding a small amount of the chiral phenyl isocyanide with both monomer and chiral inducer functions for the formation of CLC from a nematic liquid crystal. Polymerization of the isocyanide monomer in the chiral liquid crystal reaction field prepared via chiral induction by itself produced poly(phenyl isocyanide) (PPI) with a one-handed helical structure. The asymmetric polymerization of the chiral monomer in CLC amplifies optical activity for the resultant polymer. The polymer thus prepared shows liquid crystallinity. Further, a magnetic orientation in the solvent vapor environment of the poly(phenyl isocyanides) was achieved. Synchrotron X-ray analysis evaluated the uniaxial orientation of PPI.

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Controlled Synthesis of Cyclic‐Helical Polymers with Circularly Polarized Luminescence

Cited by 7 publications

References 57 publications

Cyclic vs Linear Bottlebrush Polymers in Solution: Side-Chain Length Effect

Cyclic vs Linear Bottlebrush Polymers in Solution: Side-Chain Length Effect

Polyfluorene-block-poly(phenyl isocyanide) Copolymers: One-Pot Synthesis, Helical Assembly, and Circularly Polarized Luminescence

Self-Inductive Asymmetric Synthesis of Polyisocyanides in Liquid Crystal

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