Precise Control of Two-Dimensional Hexagonal Platelets via Scalable, One-Pot Assembly Pathways Using Block Copolymers with Crystalline Side Chains

Teng, Feiyang; Xiang, Bingbing; Liu, Liping; Varlas, Spyridon; Tong, Zaizai

doi:10.1021/jacs.3c09370

Cited by 11 publications

(5 citation statements)

References 62 publications

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“…Following pioneering studies by Manners and Winnik, crystallization-driven self-assembly (CDSA) is now well-established as a synthetic route to highly anisotropic block copolymer rods and other interesting morphologies such as diamond-like platelets. − CDSA typically utilizes an insoluble crystalline block and a soluble steric stabilizer block. Most studies are conducted at high dilution in a range of organic solvents, but CDSA can also be achieved in (dilute) aqueous solution, which is preferred for potential bioapplications. ,− …”

Section: Introductionmentioning

confidence: 99%

Combining Crystallization-Driven Self-Assembly with Reverse Sequence Polymerization-Induced Self-Assembly Enables the Efficient Synthesis of Hydrolytically Degradable Anisotropic Block Copolymer Nano-objects Directly in Concentrated Aqueous Media

Farmer,

Musa,

Armes

2024

J. Am. Chem. Soc.

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Herein we combine the well-known processing advantages conferred by polymerization-induced self-assembly (PISA) with crystallization-driven self-assembly (CDSA) to achieve the efficient synthesis of hydrolytically degradable, highly anisotropic block copolymer nano-objects directly in aqueous solution at 30% w/w solids. This new strategy involves a so-called reverse sequence PISA protocol that employs poly(L-lactide) (PLLA) as the crystallizable coreforming block and poly(N,N′-dimethylacrylamide) (PDMAC) as the water-soluble non-ionic coronal block. Such syntheses result in PDMAC-rich anisotropic nanoparticles. Depending on the target diblock copolymer composition, either rod-like nanoparticles or diamond-like platelets can be obtained. Furthermore, N-Acryloylmorpholine is briefly evaluated as an alternative hydrophilic vinyl monomer to DMAC. Given that the PLLA block can undergo either hydrolytic or enzymatic degradation, such nanoparticles are expected to offer potential applications in various fields, including nextgeneration sustainable Pickering emulsifiers.Recently, we reported a reverse sequence PISA formulation based on a hydrophobic poly(ε-caprolactone) (PCL) precursor, which exhibits a melting transition, T m , at approximately 50 °C. In this prior study, the in situ DMAC polymerization was performed at 80 °C, which results in the formation of spherical PCL−PDMAC nanoparticles with amorphous cores. 23 In contrast, PLLA has a T m of 114−153 °C (see Figure S1). Hence reverse sequence PISA syntheses performed at 70 °C should lead to the formation of anisotropic PLLA-PDMAC nanoparticles with semicrystalline cores via CDSA (see Scheme 1).

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Section: Introductionmentioning

confidence: 99%

Combining Crystallization-Driven Self-Assembly with Reverse Sequence Polymerization-Induced Self-Assembly Enables the Efficient Synthesis of Hydrolytically Degradable Anisotropic Block Copolymer Nano-objects Directly in Concentrated Aqueous Media

Farmer,

Musa,

Armes

2024

J. Am. Chem. Soc.

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“…Although 1D D–A nanostructures were initially prepared from small molecules, the lack of length controllability or the need for complicated processing (e.g., vacuum deposition at high temperatures) has limited their practicality. , On the other hand, π-conjugated polymers (CPs) are excellent for their solution processability, such as roll-to-roll process, thus providing maximum process efficiency. , Especially, the crystallization-driven self-assembly (CDSA), pioneered by the Manners group, has enabled the formation of various nanostructures (micelles, nanofibers, nanosheets, etc.) and precisely controlled their sizes from CPs, thereby significantly enhancing their applicability. − Furthermore, our group recently developed a novel strategy of the in situ nanoparticlization of conjugated polymers (INCP) containing various crystalline donor moieties (e.g., polyacetylene, polythiophene, and poly(phenylenevinylene)), where polymerization and self-assembly into various nanostructures occurred simultaneously, eliminating the need for any postprocessing and highlighting greater potential of CPs. − Despite the elegant demonstration and success on CDSA and INCP strategies, their scope has been primarily limited to insulating polymer shell blocks, such as polystyrene or poly(ethylene glycol), , or with just a few examples of those containing only donor CPs and shells (Figure a). ,− Therefore, the fabrication of unprecedented 1D nanostructures from fully conjugated D–A block copolymers (BCPs) remains a highly desired goal.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Preparation of Length and Width-Controllable Donor–Acceptor Nanoribbons via Polymerization-Induced Crystallization-Driven Self-Assembly of Fully Conjugated Block Copolymers

Kim,

Lee,

Hwang

et al. 2024

J. Am. Chem. Soc.

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Despite the high potential of one-dimensional (1D) donor−acceptor (D−A) coaxial nanostructures in bulk-heterojunction solar cell applications, the preparation of such 1D nanostructures using π-conjugated polymers has remained elusive. Herein, we demonstrate the first example of D−A semiconducting nanoribbons based on fully conjugated block copolymers (BCPs) prepared in a highly efficient procedure with controllable width and length via living crystallization-driven self-assembly (CDSA). Initially, Suzuki−Miyaura catalyst-transfer polymerization was employed to successfully synthesize BCPs containing two types of acceptor shells as the first block, followed by a donor poly(3propylthiophene) core as the second block. The limited solubility and high crystallinity of the core induced a polymerization-induced crystallization-driven self-assembly (PI-CDSA) of the BCPs into nanoribbons during polymerization, providing a tunable width (7.6−39.6 nm) depending on the length of the polymer backbone. Surprisingly, purifying as-synthesized BCPs via simple precipitation directly yielded short and uniform seed structures, greatly shortening the overall protocol by eliminating the timeconsuming process of initial aging and breaking down to the seed required for the conventional CDSA. With this new highly efficient method, we achieved length control over a broad range from 169 to 2210 nm, with high precision (L w /L n < 1.20). Furthermore, combining self-seeding and seeded growth from two different D−A-type BCPs enabled continuous living epitaxial growth from each end of the nanoribbons, resulting in B-A-B triblock D−A semiconducting comicelles with controlled length.

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“…In recent years, with the advantage of precise morphology control, self-assembled 2D materials with thickness at least 1 order of magnitude smaller than the lateral size are showing great potential in template patterning, − optoelectronics, bionics, and selective local degradation in a rather different way from covalent 2D materials. Both the lateral size and the number of layers in the thickness direction are important morphological parameters.…”

mentioning

confidence: 99%

“…Both the lateral size and the number of layers in the thickness direction are important morphological parameters. In addition to precisely controllable lateral size through “living” growth, − ,, the varying number of stacked layers will lead to distinct different properties, e.g., in conjugated polymer crystals with controllable conductivity . Some peculiar phenomena associated with the multilayer stacking of covalent planar materials have been discovered and have become hot topics.…”

mentioning

confidence: 99%

In Situ Monitoring and Tuning Multilayer Stacking of Polymer Lamellar Crystals in Solution with Aggregation-Induced Emission

Liu,

Pan,

et al. 2024

Nano Lett.

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Many types of self-assembled 2D materials with fascinating morphologies and novel properties have been prepared and used in solution. However, it is still a challenge to monitor their in situ growth in solution and to control the number of layers in these materials. Here, we demonstrate that the aggregation-induced emission (AIE) effect can be applied for the in situ decoupled tracing of the lateral growth and multilayer stacking of polymer lamellar crystals in solution. Multilayer stacking considerably enhances the photoluminescence intensity of the AIE molecules sandwiched between two layers of lamellar crystals, which is 2.4 times that on the surface of monolayer crystals. Both variation of the self-seeding temperature of crystal seeds and addition of a trace amount of long polymer chains during growth can control multilayer lamellar stacking, which are applied to produce tunable fluorescent patterns for functional applications.

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Precise Control of Two-Dimensional Hexagonal Platelets via Scalable, One-Pot Assembly Pathways Using Block Copolymers with Crystalline Side Chains

Cited by 11 publications

References 62 publications

Combining Crystallization-Driven Self-Assembly with Reverse Sequence Polymerization-Induced Self-Assembly Enables the Efficient Synthesis of Hydrolytically Degradable Anisotropic Block Copolymer Nano-objects Directly in Concentrated Aqueous Media

Combining Crystallization-Driven Self-Assembly with Reverse Sequence Polymerization-Induced Self-Assembly Enables the Efficient Synthesis of Hydrolytically Degradable Anisotropic Block Copolymer Nano-objects Directly in Concentrated Aqueous Media

Highly Efficient Preparation of Length and Width-Controllable Donor–Acceptor Nanoribbons via Polymerization-Induced Crystallization-Driven Self-Assembly of Fully Conjugated Block Copolymers

In Situ Monitoring and Tuning Multilayer Stacking of Polymer Lamellar Crystals in Solution with Aggregation-Induced Emission

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