Crystallization-Driven Self-Assembly toward Uniform Nanofibers Containing a Donor–Acceptor Core with Near-Infrared Absorption/Emission, Photodynamic, and Photothermal Activities: A Small Variation on the Structure of Donor–Acceptor Segment Matters

Ma, Junyu; Huang, Fengfeng; Zhang, Sen; Ye, Jing; Huang, Xiaoyu; Lu, Guolin; Feng, Chun

doi:10.1021/acs.macromol.3c00781

Cited by 4 publications

(1 citation statement)

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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.…”

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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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