Charge-Transfer-Induced Self-Assembly of Doped Conjugated Block Copolymer Nanofibers

Narasimha, Karnati; Albert, Shine K.; Kim, Jong-Wook; Kang, Hyojung; Kang, Sungsu; Park, Jungwon; Park, JaeHong; Park, So‐Jung

doi:10.1021/acsmacrolett.2c00752

Cited by 4 publications

(4 citation statements)

References 47 publications

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“…Self-assembly of conjugated, semiconducting organic polymers is of intense current interest due to their ability to form functional one-dimensional (1D) nanofibers for optoelectronic applications. − Conjugated polymers have large absorption cross sections and can exhibit highly efficient energy transfer which makes them excellent candidates for light harvesting, light-emitting, photovoltaic, and photodetection applications. − Nanofiber properties are dependent on their length and chemical composition, and exerting control over these factors is crucial for maximizing optoelectronic performance. , …”

Section: Introductionmentioning

confidence: 99%

Homogeneous and Segmented Nanofibers with a Conjugated Poly[3-(2′-ethylhexyl)thiophene] Core via Living Crystallization-Driven Self-Assembly

Vespa,

Hudson,

Manners

2024

Macromolecules

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The ambient temperature living crystallizationdriven self-assembly (CDSA) seeded growth method for polymeric amphiphiles with a crystallizable core-forming block has emerged as a promising approach to morphologically pure samples of uniform, length-controlled one-dimensional nanofibers as well as more complex architectures such as segmented assemblies. Access to nanofibers with poly(3-hexylthiophene) (P3HT) as the coreforming block is highly desirable as a result of their optoelectronic properties. However, application of the living CDSA method to P3HT diblock copolymers has proven to be a challenge due to rapid P3HT crystallization. This causes uncontrolled homogeneous nucleation and defect formation, resulting in a loss of length control and increased nanofiber length dispersity. Herein, we have explored the replacement of the P3HT core-forming block with a more soluble poly[3-(2′-ethylhexyl)thiophene] (P3EHT) core and demonstrate improved control over nanofiber formation. Specifically, we have studied two P3EHT-containing diblock copolymers, P3EHT 23 -b-PEG 113 [PEG = poly(ethylene glycol)] and P3EHT 19 -b-P2VP 138 [P2VP = poly(2-vinylpyridine)]. Seeded growth of P3EHT 19 -b-P2VP 138 nanofibers at 22 °C produced low dispersity nanofibers with length control up to ∼1 μm, while P3EHT 23 -b-PEG 113 only provided length control up to ∼300 nm under similar conditions. Self-nucleation was postulated to impair efficient seeded growth of P3EHT 23 -b-PEG 113 and solution-state variable temperature UV−vis spectroscopy was used to locate temperatures where self-nucleation was suppressed. These studies revealed that homogeneous nucleation is suppressed for at least 24 h at or above 30 °C for P3EHT 23 -b-PEG 113 in a 1:1 n-butanol:methanol solution. In the case of P3EHT 23 -b-PEG 113 , this allowed us to efficiently perform seeded growth under conditions (≥30 °C) that resulted in the formation of near-uniform nanofibers with controlled lengths of up to ∼1 μm. Self-nucleation suppression was also successfully utilized during thermal self-seeding experiments, wherein P3EHT 23 -b-PEG 113 nanofibers with controlled lengths up to 2.8 μm and low length dispersities were formed. Seeded growth of P3EHT 19 -b-P2VP 138 from the termini of P3EHT 23 -b-PEG 113 seeds at 22 °C provided access to well-defined B-A-B triblock comicelles with a segmented coronal structure.

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Section: Introductionmentioning

confidence: 99%

Homogeneous and Segmented Nanofibers with a Conjugated Poly[3-(2′-ethylhexyl)thiophene] Core via Living Crystallization-Driven Self-Assembly

Vespa,

Hudson,

Manners

2024

Macromolecules

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“…Synthesizing block copolymers composed of blocks that cannot be prepared via the same mechanism is very complicated. Generally, the strategies include (1) connecting the chain ends of two preformed homopolymers, for example, coupling the alkyne-terminated poly(3-hexylthiophene) (P3HT-alkyne) with azide-terminated poly(ethylene oxide) (PEO-N 3 ) via copper-catalyzed azide–alkyne cycloaddition, which generated P3HT- b -PEO copolymer (Figure a); and (2) functionalizing a homopolymer with an active terminal followed by the chain-extension with a second monomer; for example, P3HT was bonded with a hydroxyl (P3HT-OH) group followed by initiating the copolymerization of l -lactide, which resulted in P3HT- b -poly( l -lactic acid) (P3HT- b -PLA) copolymer (Figure b) . These strategies are time-consuming and require tedious synthesis procedures.…”

Section: Introductionmentioning

confidence: 99%

“…Among the reported π-conjugated polymers, polythiophenes (PTs), , poly(phenyleneethynylene)s (PPEs), , and polyfluorenes (PFs) − are widely investigated due to their high conductivity and adjustable optoelectronic characteristics. These polymers with controllable molar mass ( M n ) and narrow molecular weight distribution ( M w / M n ) are commonly prepared through the “living catalyst transfer polycondensation (CTP)”, which involve Kumada, Sonogashira, and Suzuki cross-coupling reactions using Ni(II) or Pd(II) catalysts. , Recently, we have developed a series of Pd(II) and Ni(II) catalysts, which can initiate the living polymerization of phenyl isocyanides (PIs), allenes, and dizaoacetates, and enable the controlled synthesis of helical poly(phenyl isocyanide) (PPI), − polyallene (PA), ,,− and polycarbene (PC), respectively. ,− Combining these polymerizations with CTP, block copolymers such as PT- b -PPI, − PT- b -PA, − PT- b -PC, PPE- b -PPI, , PF- b -PPI, , and PF- b -PC have been prepared via the one-pot living block copolymerization of two distinct monomers (Figure c).…”

Section: Introductionmentioning

confidence: 99%

“…To overcome these issues, one possible way is to prepare block copolymers using a single catalyst, which can provide sequential and one-pot growth of two mechanistically distinct polymers. Among the reported π-conjugated polymers, polythiophenes (PTs), 20,21 poly(phenyleneethynylene)s (PPEs), 22,23 and polyfluorenes (PFs) 24−26 are widely investigated due to their high conductivity and adjustable optoelectronic characteristics. These polymers with controllable molar mass (M n ) and narrow molecular weight distribution (M w /M n ) are commonly prepared through the "living catalyst transfer polycondensation (CTP)", which involve Kumada, Sonogashira, and Suzuki cross-coupling reactions using Ni(II) or Pd(II) catalysts.…”

Section: Introductionmentioning

confidence: 99%

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

Liu,

Gao,

2023

Acc. Chem. Res.

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

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

Zhou,

Chen,

Zhou

et al. 2023

Chem. Res. Chin. Univ.

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Charge-Transfer-Induced Self-Assembly of Doped Conjugated Block Copolymer Nanofibers

Cited by 4 publications

References 47 publications

Homogeneous and Segmented Nanofibers with a Conjugated Poly[3-(2′-ethylhexyl)thiophene] Core via Living Crystallization-Driven Self-Assembly

Homogeneous and Segmented Nanofibers with a Conjugated Poly[3-(2′-ethylhexyl)thiophene] Core via Living Crystallization-Driven Self-Assembly

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

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

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