Synthesis and living crystallization-driven self-assembly of backbone asymmetric and symmetric π-conjugated oligo(<i>p</i>-phenylene ethynylene)-based block copolymers

Nie, Jiucheng; Huang, Xiaoyu; Lu, Guolin; Winnik, Mitchell A.; Feng, Chuanqi

doi:10.1039/d2py01225a

Cited by 7 publications

(3 citation statements)

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“…The percentages of surviving seeds at each annealing temperature ( P seed,T ) were estimated by L n,T of formed micelles and L n,seed of initial seeds ( P seed,T = L n,seed / L n,T , Tables S1–S2). ,, The exponential relationship between the percentage of surviving seeds and annealing temperature for both samples of b -T-OPE 4 -DPP-OPE 4 - b -P2VP 44 and l -P-OPE 4 -DPP-OPE 4 - b -P2VP 44 revealed the key characteristic of the self-seeding process (Figure F). − One can note that the resistance of seed micelles of b -T-OPE 4 -DPP-OPE 4 - b -P2VP 44 toward the dissolution upon heating is obviously stronger than that of the seed micelles of l -P-OPE 4 -DPP-OPE 4 - b -P2VP 44 . For example, the percentages of surviving seed micelles were about 52.9 and 14.8% at 62 °C for b -T-OPE 4 -DPP-OPE 4 - b -P2VP 44 and l -P-OPE 4 -DPP-OPE 4 - b -P2VP 44 , respectively.…”

Section: Results and Discussionmentioning

confidence: 94%

“…Self-seeding has emerged as a facile platform to generate uniform π-conjugated-polymer-containing fiber-like micelles. − We then examined the influence of OPE 4 -DPP-OPE 4 structure on self-seeding behaviors. Aliquots of micellar fragments of b -T-OPE 4 -DPP-OPE 4 - b -P2VP 44 , l -T-OPE 4 -DPP-OPE 4 - b -P2VP 44 , and l -P-OPE 4 -DPP-OPE 4 - b -P2VP 44 (Figure S6), which were obtained by sonication of the obtained polydisperse micelles (Figure A–C), were subjected to annealing at different temperatures, followed by cooling/aging at 25 °C for 24 h (Figure A).…”

Section: Results and Discussionmentioning

confidence: 99%

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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,

Huang,

Zhang

et al. 2023

Macromolecules

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Although living crystallization-driven self-assembly (CDSA) has emerged as a facile approach to generate uniform πconjugated-polymer-based fiber-like micelles, the extension of living CDSA to prepare uniform donor−acceptor (D−A) fiber-like micelles of controlled length with attractive near-infrared (NIR) absorption/emission, photodynamic (PD), and photothermal (PT) properties is virtually unexplored. Herein, three block copolymers composed of the same corona-forming P2VP 44 (P2VP = poly(2vinylpyridine), the subscript is the degree of polymerization) but different D−A π-conjugated core-forming co-oligomers of OPE 4 -DPP-OPE 4 (OPE 4 = oligo(p-phenylene ethynylene), DPP = diketopyrrolopyrrole) are designed and synthesized to probe the steric and electronic effect of co-oligomers of OPE 4 -DPP-OPE 4 on their CDSA behaviors and photophysical properties. One cooligomer contains a DPP with two 2-ethylhexyl side chains flanked by two thiophene-OPE 4 segments (b-T-OPE 4 -DPP-OPE 4 ). The variation of the second one is the replacement of 2-ethylhexyl side chains with linear octyls (l-T-OPE 4 -DPP-OPE 4 ). The last one is composed of a DPP with two linear octyl side chains flanked by two phenylene-OPE 4 segments (l-P-OPE 4 -DPP-OPE 4 ). Uniform fiber-like micelles can be generated by a self-seeding approach for b-T-OPE 4 -DPP-OPE 4 -b-P2VP 44 and l-P-OPE 4 -DPP-OPE 4 -b-P2VP 44 , whereas polydisperse fiber-like micelles only can be obtained for l-T-OPE 4 -DPP-OPE 4 -b-P2VP 44 likely due to the multiple packing modes of l-T-OPE 4 -DPP-OPE 4 . Intriguingly, the aging of micelles of l-T-OPE 4 -DPP-OPE 4 -b-P2VP 44 can promote the conversion of the packing mode of l-T-OPE 4 -DPP-OPE 4 units to their most thermodynamically stable packing mode, and thus, selfseeding of aged seed micelles of l-T-OPE 4 -DPP-OPE 4 -b-P2VP 44 gave uniform fiber-like micelles of controlled length. More interestingly, micellar solution of b-T-OPE 4 -DPP-OPE 4 -b-P2VP 44 exhibits NIR absorption/emission, PT, and PD activities upon the light irradiation at 660 nm. Although micellar solution of l-T-OPE 4 -DPP-OPE 4 -b-P2VP 44 also shows NIR absorption/emission and PT activity, its PD activity is much lower relative to that of b-T-OPE 4 -DPP a -OPE 4 -b-P2VP 44 . The micellar solution of l-P-OPE 4 -DPP-OPE 4 -b-P2VP 44 exhibits neither NIR absorption/emission nor PT/PD activities upon the light irradiation at 660 nm. All these results showed that a small variation of structure of OPE 4 -DPP-OPE 4 can lead to distinct CDSA behaviors and absorption/emission/ PD/PT properties.

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Section: Results and Discussionmentioning

confidence: 94%

Section: Results and Discussionmentioning

confidence: 99%

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,

Huang,

Zhang

et al. 2023

Macromolecules

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“…[14][15][16][17][18][19][20][21][22] Until recent decades, the living crystallization-driven selfassembly (CDSA) of coil-crystalline BCPs in solution has emerged as a robust strategy to realize the fabrication of a large variety of fiber-like nano-and meso-structures (micelles) with precisely controlled morphology, dimension, composition and functionality. [23][24][25][26][27][28][29][30] The crystallization of a core-forming block, the predominant driving force for the self-assembly process, provides the possibility of achieving strong kinetic control over the evolution of fiber-like micelles. From the kinetic point of view, by deliberately separating nucleation and growth stages in the micellar elongation process, the formation of fiber-like micelles can proceed in a controlled way to give uniform fiber-like micelles with precise length/ composition.…”

Section: Introductionmentioning

confidence: 99%

Modulating living crystallization-driven self-assembly behaviors of oligo(p-phenylene ethynylene)-containing block copolymers and micellar stability by solvent and corona-forming chain length

et al. 2023

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Sterisch erlaubte Supramolekulare Polymerisationen des H‐Typs

Manha Veedu,

Niemeyer,

Bäumer

et al. 2023

Angewandte Chemie

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The functionalization of pi‐conjugated scaffolds with sterically demanding substituents is a widely used tactic to suppress cofacial (H‐type) stacking interactions, which may even inhibit self‐assembly. Contrary to expectations, we demonstrate herein that increasing steric effects can result in an enhanced thermodynamic stability of H‐type supramolecular polymers. In our approach, we have investigated two boron dipyrromethene (BODIPY) dyes with bulky phenyl (2) and mesityl (3) meso‐substituents and compared their self‐assembly in nonpolar media with that of a parent meso‐methyl BODIPY 1 lacking bulky groups. While the enhanced steric demand induces pathway complexity, the superior thermodynamic stability of the H‐type pathways can be rationalized in terms of additional enthalpic gain arising from intermolecular C‐H···F‐B interactions of the orthogonally arranged aromatic substituents, which overrule their inherent steric demand. Our findings underline the importance of balancing competing non‐covalent interactions in self‐assembly.

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Synthesis and living crystallization-driven self-assembly of backbone asymmetric and symmetric π-conjugated oligo(p-phenylene ethynylene)-based block copolymers

Abstract: The backbone symmetry of π-conjugated segments is one of the most important structural factors that affect their crystalline behaviors. However, the influence of backbone symmetry of π-conjugated blocks on living...

Cited by 7 publications

References 58 publications

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

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

Modulating living crystallization-driven self-assembly behaviors of oligo(p-phenylene ethynylene)-containing block copolymers and micellar stability by solvent and corona-forming chain length

Sterisch erlaubte Supramolekulare Polymerisationen des H‐Typs

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