Defect-Induced Secondary Crystals Drive Two-Dimensional to Three-Dimensional Morphological Evolution in the Co-Self-Assembly of Polyferrocenylsilane Block Copolymer and Homopolymer

Jiang, Jingjie; Nikbin, Ehsan; Liu, Yang; Lei, Shixing; Ye, Gang; Howe, Jane Y.; Manners, Ian; Winnik, Mitchell A.

doi:10.1021/jacs.3c09791

“…In addition, they feature pronounced secondary crystals located predominantly near the ends of the platelet core, creating a high-contrast appearance (see Figure d). Secondary crystals nucleate from defects on the basal surface of the micelles . In comparison, micelles (Figure e,f) formed from the 0.6 μm seeds exhibit traces of secondary crystals, while those (Figure a,b) generated from 1.6 μm seeds show only rare occurrences of secondary crystals.…”

Section: Resultsmentioning

confidence: 90%

“…Based on our experience, the secondary crystallization observed here originates from the presence of crystal defects promoted by the rapid crystallization of PFS 65 - b -PI 390 -NH 2 either with or without the second PFS BCP. We have shown that when this type of structure is treated with BCPs at high degrees of supersaturation, it is possible to form spherulites and their precursors . Thus, we used the 2D structures formed by PFS 65 - b -PI 390 -NH 2 (Figure d) as seeds and added concentrated solutions of PFS 65 - b -PI 390 -NH 2 in THF to the seed solution at unimer-to-seed mass ratios of 20:1, 40:1, 200:1, and 600:1.…”

Section: Resultsmentioning

confidence: 99%

“…Most of the platelet@fiber structures observed here have secondary crystals on their basal surfaces. We previously reported that these secondary crystals are critical intermediates for spherulite formation. , In order to test this idea, we carried out multistep seeded growth experiments, adding more PFS 65 - b -PI 390 -NH 2 unimers to achieve higher supersaturation degrees in decane. In agreement with previous results, we found that the micelles evolved from platelet@fibers, to hedrites, sheaves, and finally spherulites.…”

Section: Discussionmentioning

confidence: 99%

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Crystallization-Driven Self-Assembly of Polyferrocenyldimethylsilane Block Copolymers with the Corona Modified with Pendant Amino Groups

Jiang,

Nikbin,

Plaha

et al. 2024

Macromolecules

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Polyferrocenyldimethylsilane-block-polyisoprene (PFS-b-PI) with a PI block much longer than the PFS block typically forms one-dimensional (1D) rod-like micelles in a selective solvent like decane. Here, we test the idea that introducing polar amino groups into the PI block (ca. 10 mol % via a thiol–ene reaction) would reduce the corona dimensions in decane and promote the formation of 2D assemblies. For example, PFS65-b-PI390-NH2 formed ribbon-like micelles when added as a unimer to rod-like PFS44-b-PMVS250 (PMVS = polymethylvinylsiloxane) micelles as seeds in decane. Elongated platelets with fiber-like protrusions from the ends were formed when PFS65-b-PI390-NH2 was combined with a second block copolymer (BCP) and added to the rod-like seed micelles. In the co-self-assembly of PFS65-b-PI390-NH2 and PFS25-b-PI1000 or PFS50-b-PI1000, we varied the mass ratio from 3:7 to 1:1 and 7:3, leading to platelet@fiber structures with increased length and width. A similar phenomenon was seen in mixed micelles of PFS65-b-PI390-NH2 with PFS35-b-PI273 or PFS38-b-PI850. As the PFS65-b-PI390-NH2 content in the BCP blends was increased from 30% by mass to 70%, the widths of the micelles nearly doubled. We explain this effect in terms of the influence of the amino groups on the corona chain dimensions: BCP mixtures with a larger fraction of corona chains bearing amino groups led to contracted corona dimensions, promoting epitaxial growth of unimers on the lateral edges of the micelles. If the second BCP had a long corona-forming block, then increasing amounts of this block led to longer micelles that were somewhat narrower in width. Here, the long corona chains suppress epitaxial growth along the lateral edge of the micelles. The introduction of polar amino groups into the PI block of PFS-b-PI BCPs led to new types of uniform structures by CDSA. Many of the 2D assemblies that we prepared had secondary crystals on their basal surfaces. We showed that adding PFS65-b-PI390-NH2 unimer at high supersaturation to these micelles as seeds led to 3D assemblies associated with spherulite formation. In addition, direct self-assembly of each of the three PFS-b-PI-NH2 BCPs also formed spherulites and their precursors.

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“…Living self-assembly has been an active area of supramolecular self-assembly research, which has raised the precise control of nanostructures to unprecedented levels and made it possible to fabricate complex structures that had never been achieved before. [1][2][3][4][5][6][7][8][9][10][11][12] In order to achieve this self-assembly control, several living self-assembly methods have been developed. These methods mainly include crystallization-driven living self-assembly of polymers [13][14][15][16] and kinetically trapping of small molecules in metastable aggregates or an inactive molecular states.…”

mentioning

confidence: 99%

Light‐Regulated Nucleation for Growing Highly Uniform Single‐Crystalline Microrods

Sun,

Gong,

Che

et al. 2024

Angewandte Chemie

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We report a light‐irradiation method to control the synchronous nucleation of a donor‐acceptor (D‐A) fluorophore for growing highly uniform single‐crystalline microrods, which is in sharp contrast to the prevailing methods of inhibiting spontaneous nucleation and additionally adding seeds. The D‐A fluorophore was observed to undergo photoinduced electron transfer to CrCl3, leading to the generation of HCl and the subsequent protonation of the D‐A fluorophore. By intensifying photoirradiation or prolonging its duration, the concentration of protonated D‐A fluorophores can be rapidly increased to a high supersaturation level. This results in the formation of a controlled number of nuclei in a synchronous manner, which in turn kickstart the epitaxial growth of protonated D‐A fluorophores towards uniform single‐crystalline microrods of controlled sizes. The light‐regulated synchronous nucleation and uniform growth of microrods are a unique phenomenon that can only be achieved by specific Lewis acids, making it a novel probing method for sensitively detecting strong Lewis acids such as chromium chloride.

show abstract

“…Living self-assembly has been an active area of supramolecular self-assembly research, which has raised the precise control of nanostructures to unprecedented levels and made it possible to fabricate complex structures that had never been achieved before. [1][2][3][4][5][6][7][8][9][10][11][12] In order to achieve this self-assembly control, several living self-assembly methods have been developed. These methods mainly include crystallization-driven living self-assembly of polymers [13][14][15][16] and kinetically trapping of small molecules in metastable aggregates or an inactive molecular states.…”

mentioning

confidence: 99%

Light‐Regulated Nucleation for Growing Highly Uniform Single‐Crystalline Microrods

Sun,

Gong,

Che

et al. 2024

Angew Chem Int Ed

0

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We report a light‐irradiation method to control the synchronous nucleation of a donor‐acceptor (D‐A) fluorophore for growing highly uniform single‐crystalline microrods, which is in sharp contrast to the prevailing methods of inhibiting spontaneous nucleation and additionally adding seeds. The D‐A fluorophore was observed to undergo photoinduced electron transfer to CrCl3, leading to the generation of HCl and the subsequent protonation of the D‐A fluorophore. By intensifying photoirradiation or prolonging its duration, the concentration of protonated D‐A fluorophores can be rapidly increased to a high supersaturation level. This results in the formation of a controlled number of nuclei in a synchronous manner, which in turn kickstart the epitaxial growth of protonated D‐A fluorophores towards uniform single‐crystalline microrods of controlled sizes. The light‐regulated synchronous nucleation and uniform growth of microrods are a unique phenomenon that can only be achieved by specific Lewis acids, making it a novel probing method for sensitively detecting strong Lewis acids such as chromium chloride.

show abstract

Defect-Induced Secondary Crystals Drive Two-Dimensional to Three-Dimensional Morphological Evolution in the Co-Self-Assembly of Polyferrocenylsilane Block Copolymer and Homopolymer

Cited by 8 publications

References 103 publications

Crystallization-Driven Self-Assembly of Polyferrocenyldimethylsilane Block Copolymers with the Corona Modified with Pendant Amino Groups

Crystallization-Driven Self-Assembly of Polyferrocenyldimethylsilane Block Copolymers with the Corona Modified with Pendant Amino Groups

Light‐Regulated Nucleation for Growing Highly Uniform Single‐Crystalline Microrods

Light‐Regulated Nucleation for Growing Highly Uniform Single‐Crystalline Microrods

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