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Subtle Molecular Changes Largely Modulate Chiral Helical Assemblies of Achiral Conjugated Polymers by Tuning Solution-State Aggregation
[Image: see text] Understanding the solution-state aggregate structure and the consequent hierarchical assembly of conjugated polymers is crucial for controlling multiscale morphologies during solid thin-film deposition and the resultant electronic properties. However, it remains challenging to comp...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10683494/ https://www.ncbi.nlm.nih.gov/pubmed/38033802 http://dx.doi.org/10.1021/acscentsci.3c00775 |
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author | Park, Kyung Sun Luo, Xuyi Kwok, Justin J. Khasbaatar, Azzaya Mei, Jianguo Diao, Ying |
author_facet | Park, Kyung Sun Luo, Xuyi Kwok, Justin J. Khasbaatar, Azzaya Mei, Jianguo Diao, Ying |
author_sort | Park, Kyung Sun |
collection | PubMed |
description | [Image: see text] Understanding the solution-state aggregate structure and the consequent hierarchical assembly of conjugated polymers is crucial for controlling multiscale morphologies during solid thin-film deposition and the resultant electronic properties. However, it remains challenging to comprehend detailed solution aggregate structures of conjugated polymers, let alone their chiral assembly due to the complex aggregation behavior. Herein, we present solution-state aggregate structures and their impact on hierarchical chiral helical assembly using an achiral diketopyrrolopyrrole-quaterthiophene (DPP-T4) copolymer and its two close structural analogues wherein the bithiophene is functionalized with methyl groups (DPP-T2M2) or fluorine atoms (DPP-T2F2). Combining in-depth small-angle X-ray scattering analysis with various microscopic solution imaging techniques, we find distinct aggregate in each DPP solution: (i) semicrystalline 1D fiber aggregates of DPP-T2F2 with a strongly bound internal structure, (ii) semicrystalline 1D fiber aggregates of DPP-T2M2 with a weakly bound internal structure, and (iii) highly crystalline 2D sheet aggregates of DPP-T4. These nanoscopic aggregates develop into lyotropic chiral helical liquid crystal (LC) mesophases at high solution concentrations. Intriguingly, the dimensionality of solution aggregates largely modulates hierarchical chiral helical pitches across nanoscopic to micrometer scales, with the more rigid 2D sheet aggregate of DPP-T4 creating much larger pitch length than the more flexible 1D fiber aggregates. Combining relatively small helical pitch with long-range order, the striped twist-bent mesophase of DPP-T2F2 composed of highly ordered, more rigid 1D fiber aggregate exhibits an anisotropic dissymmetry factor (g-factor) as high as 0.09. This study can be a prominent addition to our knowledge on a solution-state hierarchical assembly of conjugated polymers and, in particular, chiral helical assembly of achiral organic semiconductors that can catalyze an emerging field of chiral (opto)electronics. |
format | Online Article Text |
id | pubmed-10683494 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-106834942023-11-30 Subtle Molecular Changes Largely Modulate Chiral Helical Assemblies of Achiral Conjugated Polymers by Tuning Solution-State Aggregation Park, Kyung Sun Luo, Xuyi Kwok, Justin J. Khasbaatar, Azzaya Mei, Jianguo Diao, Ying ACS Cent Sci [Image: see text] Understanding the solution-state aggregate structure and the consequent hierarchical assembly of conjugated polymers is crucial for controlling multiscale morphologies during solid thin-film deposition and the resultant electronic properties. However, it remains challenging to comprehend detailed solution aggregate structures of conjugated polymers, let alone their chiral assembly due to the complex aggregation behavior. Herein, we present solution-state aggregate structures and their impact on hierarchical chiral helical assembly using an achiral diketopyrrolopyrrole-quaterthiophene (DPP-T4) copolymer and its two close structural analogues wherein the bithiophene is functionalized with methyl groups (DPP-T2M2) or fluorine atoms (DPP-T2F2). Combining in-depth small-angle X-ray scattering analysis with various microscopic solution imaging techniques, we find distinct aggregate in each DPP solution: (i) semicrystalline 1D fiber aggregates of DPP-T2F2 with a strongly bound internal structure, (ii) semicrystalline 1D fiber aggregates of DPP-T2M2 with a weakly bound internal structure, and (iii) highly crystalline 2D sheet aggregates of DPP-T4. These nanoscopic aggregates develop into lyotropic chiral helical liquid crystal (LC) mesophases at high solution concentrations. Intriguingly, the dimensionality of solution aggregates largely modulates hierarchical chiral helical pitches across nanoscopic to micrometer scales, with the more rigid 2D sheet aggregate of DPP-T4 creating much larger pitch length than the more flexible 1D fiber aggregates. Combining relatively small helical pitch with long-range order, the striped twist-bent mesophase of DPP-T2F2 composed of highly ordered, more rigid 1D fiber aggregate exhibits an anisotropic dissymmetry factor (g-factor) as high as 0.09. This study can be a prominent addition to our knowledge on a solution-state hierarchical assembly of conjugated polymers and, in particular, chiral helical assembly of achiral organic semiconductors that can catalyze an emerging field of chiral (opto)electronics. American Chemical Society 2023-11-13 /pmc/articles/PMC10683494/ /pubmed/38033802 http://dx.doi.org/10.1021/acscentsci.3c00775 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Park, Kyung Sun Luo, Xuyi Kwok, Justin J. Khasbaatar, Azzaya Mei, Jianguo Diao, Ying Subtle Molecular Changes Largely Modulate Chiral Helical Assemblies of Achiral Conjugated Polymers by Tuning Solution-State Aggregation |
title | Subtle Molecular
Changes Largely Modulate Chiral Helical
Assemblies of Achiral Conjugated Polymers by Tuning Solution-State
Aggregation |
title_full | Subtle Molecular
Changes Largely Modulate Chiral Helical
Assemblies of Achiral Conjugated Polymers by Tuning Solution-State
Aggregation |
title_fullStr | Subtle Molecular
Changes Largely Modulate Chiral Helical
Assemblies of Achiral Conjugated Polymers by Tuning Solution-State
Aggregation |
title_full_unstemmed | Subtle Molecular
Changes Largely Modulate Chiral Helical
Assemblies of Achiral Conjugated Polymers by Tuning Solution-State
Aggregation |
title_short | Subtle Molecular
Changes Largely Modulate Chiral Helical
Assemblies of Achiral Conjugated Polymers by Tuning Solution-State
Aggregation |
title_sort | subtle molecular
changes largely modulate chiral helical
assemblies of achiral conjugated polymers by tuning solution-state
aggregation |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10683494/ https://www.ncbi.nlm.nih.gov/pubmed/38033802 http://dx.doi.org/10.1021/acscentsci.3c00775 |
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