Helix-Induced Asymmetric Self-Assembly of π-Conjugated Block Copolymers: From Controlled Syntheses to Distinct Properties

Accounts of Chemical Research, Год журнала: 2023, Номер 56(21), С. 2954 - 2967

Опубликована: Окт. 18, 2023

Conspectusπ-Conjugated polymers have gained significant interest because of their potential applications in optoelectronics, bioelectronics, and other domains. The controlled synthesis π-conjugated block optimizes performance enables novel properties functions. However, precise control the self-assembled architectures remains a formidable challenge. Inspired by helical biomacromolecules, supramolecular assemblies attention. Helical with an excess one-handed helicity can be optically active strong tendency toward self-assembly. Incorporating polymer into induce asymmetric assemblies, leading to chiral materials unique functionalities.To self-assembly architectures, are usually synthesized copolymers incorporating self-assembling characteristics. Although various been produced, is still challenging has rarely addressed. self-assembly, which transfers chirality polymer, resulting chiroptical functionalities. synthesizing hybrid containing two distinct blocks complicated. Some general strategies such as connecting chain ends preformed homopolymers extending prefabricated second monomer time-consuming require complex synthetic protocols. Therefore, developing for facile predictable molar mass, low dispersity, tunable composition practical importance.Recently, we investigated polyisocyanides, polyallenes, polycarbenes advanced Pd(II) Ni(II) catalysts. These were successfully incorporated polymers, including polythiophene, polyfluorene, poly(phenyleneethynylene), via one-pot sequential living polymerization monomers using Pd(II)- or Ni(II)-complexes As result, variety well-defined polymeric readily synthesized. copolymerized possess different structures mechanisms, copolymerization followed mechanism provided desired high yields narrow size distribution, composition.Remarkably, induces copolymer supramolecular, architecture optical properties. More interestingly, utilizing crystallization conjugated blocks, crystallization-driven helix-induced yielded family uniform single-handed dimensions, helicity. transfer rendered achiral emission white light over broad spectrum circularly polarized luminescence.

Язык: Английский

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Advances in self-assembly-based circularly polarized luminescent materials

Science China Chemistry, Год журнала: 2024, Номер 67(10), С. 3247 - 3257

Опубликована: Авг. 12, 2024

Язык: Английский

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Chiral Nanostructures from Artificial Helical Polymers: Recent Advances in Synthesis, Regulation, and Functions

ACS Nano, Год журнала: 2025, Номер 19(1), С. 229 - 280

Опубликована: Янв. 4, 2025

Helical structures such as right-handed double helix for DNA and left-handed α-helix proteins in biological systems are inherently chiral. Importantly, chirality at the nanoscopic level plays a vital role their macroscopic chiral functionalities. In order to mimic functions of natural nanoarchitectures, variety nanostructures obtained from artificial helical polymers prepared, which can be directly observed by atomic force microscopy (AFM), scanning tunneling (STM), electron (SEM), transmission (TEM). This review mainly focuses on formation morphology regulation triggered polymer chain length, concentration, solvent, temperature, photoirradiation, chemical additives. addition, distinct including recognition, circularly polarized luminescence, drug release, cell imaging, antibiosis also discussed.

Язык: Английский

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Amplified Circularly Polarized Luminescence Behavior in Chiral Co-assembled Liquid Crystal Polymer Films via the Strategic Manipulation of Chiral Inducers

ACS Applied Materials & Interfaces, Год журнала: 2024, Номер 16(20), С. 26604 - 26612

Опубликована: Май 9, 2024

One of the most important factors for future application circularly polarized luminescence (CPL) materials is their high dissymmetry (gem), and more studies are working tirelessly to focus on increasing gem value. Herein, we chose an achiral liquid crystal polymer (LC-P) two chiral binaphthyl-based inducers (R/S-3 R/S-6) with different substitution positions (3,3' R/S-3 6,6' construct co-assemblies explored induced amplification CPL behaviors. Interestingly, after thermal annealing treatment, this kind co-assembly (R/S-3)0.05-(LC-P)0.95 can emit a superior signal (|gem| = 0.31 λem 424 nm), which achieves about 13-fold in spin-coated film, compared (R/S-6)0.1-(LC-P)0.9 0.023 nm). This because could further co-assemble form ordered arrangement LC state generate regular helix nanofibers than that (R/S-6)0.1-(LC-P)0.9. work provides efficient method synthesizing high-quality CPL-active through strategic manipulation structure co-assembled LCP systems.

Язык: Английский

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Co-Assembly-Driven Chiral Induction of Well-Defined Polyfluorene-block-Poly(phenyl isocyanide) and Its Enhanced Circularly Polarized Luminescence Performance

ACS Applied Materials & Interfaces, Год журнала: 2025, Номер unknown

Опубликована: Апрель 24, 2025

Chiral induction of polyfluorene (PF)-containing block copolymers plays a crucial role in the development advanced functional materials; however, research this area remains scarce. In contribution, PFO-b-PPI diblock comprising blocks poly(9,9-dioctylfluorene) (PFO) and poly(phenyl isocyanide) (PPI) were readily synthesized one pot by combining chain-growth Suzuki cross-coupling polymerization modified 9,9-dioctylfluorene monomer with Pd(II)-catalyzed phenyl isocyanide bearing pentafluorophenyl ester substitute. The obtained possessed controlled molar mass (Mn) narrow dispersity (Mw/Mn, Đ). Meanwhile, optically active supramolecular assemblies could be formed via coassembly chiral binaphthyl-based inducer film state after thermal annealing treatment, chirality was influenced temperature weight ratio copolymer to inducer, thickness film. Further investigations revealed that exhibited morphology single-handed helical nanofibers, sense nanofibers depended on configuration inducer. Moreover, excellent circularly polarized luminescence (CPL) performance glum as high 0.11.

Язык: Английский

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Controlled Synthesis, Chiral Assembly, and Circularly Polarized Luminescence of Poly(Phenyl Isocyanide)‐Block‐Polyfluorene Copolymers

Macromolecular Rapid Communications, Год журнала: 2023, Номер 44(15)

Опубликована: Май 10, 2023

In this work, π-conjugated block copolymers consisting of poly(phenyl isocyanide) (PPI) and polyfluorene (PF) segments are facilely prepared by one-pot sequential polymerization phenyl isocyanide (monomer 1) 7-bromo-9,9-dioctylfluorene-2-boronic acid pinacol ester 2). The Pd(II)-terminated PPI is first via polymerizing monomer 1 catalyzed with alkyne-Pd(II) complex then utilized to initiate the controlled Suzuki cross-coupling 2, yielding various PPI-b-PF possessing molar mass narrow dispersity. Owing helical conformation segment structure PF segment, present distinctive optical property fascinating chiral self-assembly behavior. During process, chirality transfer from supramolecular aggregates nanofibers occurs afford optically active high activity. Furthermore, self-assembled exhibit excellent circularly polarized luminescence performance.

Язык: Английский

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Recent Advances in Helical Polyisocyanide-based Block Copolymers: Preparation, Self-assembly and Circularly Polarized Luminescence

Chemical Research in Chinese Universities, Год журнала: 2023, Номер 39(5), С. 719 - 725

Опубликована: Сен. 19, 2023

Язык: Английский

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Assembly of large-area helical nanowire and nanosphere superstructures by PS-b-P2VP/S-mandelic acid via interfacial nanoarchitectonics

Journal of Molecular Liquids, Год журнала: 2024, Номер 404, С. 125020 - 125020

Опубликована: Май 16, 2024

Язык: Английский

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Inverted and Amplified Circularly Polarized Luminescence Behavior Originated from Structure–Activity Regulation of Achiral Pyrene-Based Polymers in Chiral Coassemblies

Macromolecules, Год журнала: 2024, Номер 57(9), С. 4567 - 4575

Опубликована: Май 2, 2024

The design of excellent circularly polarized luminescence (CPL) materials with a large dissymmetry factor (glum) remains great challenge. In this paper, we chose two achiral conjugated pyrene-based main-chain polymers (BP-1 and BP-2) different substitution positions (1,6-positions the pyrene rings for BP-1 2,7-positions chiral binaphthyl-based inducer (S/R-D) bridged alkyl chain to construct coassemblies through an intermolecular chirality induction mechanism. Interestingly, after thermal annealing treatment, resulting S/R-D-BP-2 could emit inverted amplified CPL signals compared S/R-D-BP-1. Most significantly, maximum |glum| value (S/R-D)0.2-(BP-2)0.8 in spin-coated film was up 0.71 (λem = 428 nm, QY 44.8%) at 220 nm thickness, which about 6-fold that (S/R-D)0.1-(BP-1)0.9 (|glum| 0.12, λem 451 37.6%). glum due formation regular ordered helical nanofibers strong π–π stacking interactions. This work provides creative approach tune emission amplification behaviors by coassembly from polymers.

Язык: Английский

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Synthesis and self-assembly of high grafting density core-shell bottlebrush polymer with amphiphilic side chain

Reactive and Functional Polymers, Год журнала: 2024, Номер 202, С. 105997 - 105997

Опубликована: Июнь 22, 2024

Язык: Английский

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