Revealing Pathway Complexity and Helical Inversion in Supramolecular Assemblies Through Solvent‐Induced Radical Disparities
Abstract New insights are raised to interpret pathway complexity in the supramolecular assembly of chiral triarylamine tris‐amide (TATA) monomer. In cosolvent systems, the monomer undergoes entirely different assembly processes depending on the chemical feature of the two solvents. Specifically, 1,2...
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| Format: | Article |
| Language: | English |
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Wiley
2024-04-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202308371 |
| _version_ | 1797215315064520704 |
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| author | Haotian Ma Xiaoxiao Cheng Gong Zhang Tengfei Miao Zixiang He Wei Zhang |
| author_facet | Haotian Ma Xiaoxiao Cheng Gong Zhang Tengfei Miao Zixiang He Wei Zhang |
| author_sort | Haotian Ma |
| collection | DOAJ |
| description | Abstract New insights are raised to interpret pathway complexity in the supramolecular assembly of chiral triarylamine tris‐amide (TATA) monomer. In cosolvent systems, the monomer undergoes entirely different assembly processes depending on the chemical feature of the two solvents. Specifically, 1,2‐dichloroethane (DCE) and methylcyclohexane (MCH) cosolvent trigger the cooperative growth of monomers with M helical arrangement, and hierarchical thin nanobelts are further formed. But in DCE and hexane (HE) combination, a different pathway occurs where monomers go through isodesmic growth to generate twisted nanofibers with P helical arrangement. Moreover, the two distinct assemblies exhibit opposite excited‐state chirality. The driving force for both assemblies is the formation of intermolecular hydrogen bonds between amide moieties. However, the mechanistic investigation indicates that radical and neutral triarylamine species go through distinct assembly phases by changing solvent structures. The neutralization of radicals in MCH plays a critical role in pathway complexity, which significantly impacts the overall supramolecular assembly process, giving rise to inversed supramolecular helicity and distinct morphologies. This differentiation in pathways affected by radicals provides a new approach to manipulate chiral supramolecular assembly process by facile solvent–solute interactions. |
| first_indexed | 2024-04-24T11:28:07Z |
| format | Article |
| id | doaj.art-c7807b616fd240928fe24adaa80739f0 |
| institution | Directory Open Access Journal |
| issn | 2198-3844 |
| language | English |
| last_indexed | 2024-04-24T11:28:07Z |
| publishDate | 2024-04-01 |
| publisher | Wiley |
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| series | Advanced Science |
| spelling | doaj.art-c7807b616fd240928fe24adaa80739f02024-04-10T13:10:12ZengWileyAdvanced Science2198-38442024-04-011114n/an/a10.1002/advs.202308371Revealing Pathway Complexity and Helical Inversion in Supramolecular Assemblies Through Solvent‐Induced Radical DisparitiesHaotian Ma0Xiaoxiao Cheng1Gong Zhang2Tengfei Miao3Zixiang He4Wei Zhang5State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou 215123 ChinaState and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou 215123 ChinaState and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou 215123 ChinaJiangsu Key Laboratory for Chemistry of Low‐Dimensional Materials School of Chemistry and Chemical Engineering Huaiyin Normal University Huaian 223300 ChinaState and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou 215123 ChinaState and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou 215123 ChinaAbstract New insights are raised to interpret pathway complexity in the supramolecular assembly of chiral triarylamine tris‐amide (TATA) monomer. In cosolvent systems, the monomer undergoes entirely different assembly processes depending on the chemical feature of the two solvents. Specifically, 1,2‐dichloroethane (DCE) and methylcyclohexane (MCH) cosolvent trigger the cooperative growth of monomers with M helical arrangement, and hierarchical thin nanobelts are further formed. But in DCE and hexane (HE) combination, a different pathway occurs where monomers go through isodesmic growth to generate twisted nanofibers with P helical arrangement. Moreover, the two distinct assemblies exhibit opposite excited‐state chirality. The driving force for both assemblies is the formation of intermolecular hydrogen bonds between amide moieties. However, the mechanistic investigation indicates that radical and neutral triarylamine species go through distinct assembly phases by changing solvent structures. The neutralization of radicals in MCH plays a critical role in pathway complexity, which significantly impacts the overall supramolecular assembly process, giving rise to inversed supramolecular helicity and distinct morphologies. This differentiation in pathways affected by radicals provides a new approach to manipulate chiral supramolecular assembly process by facile solvent–solute interactions.https://doi.org/10.1002/advs.202308371helical inversionpathway complexityradicalssolvent–solute interactionsupramolecular assembly |
| spellingShingle | Haotian Ma Xiaoxiao Cheng Gong Zhang Tengfei Miao Zixiang He Wei Zhang Revealing Pathway Complexity and Helical Inversion in Supramolecular Assemblies Through Solvent‐Induced Radical Disparities Advanced Science helical inversion pathway complexity radicals solvent–solute interaction supramolecular assembly |
| title | Revealing Pathway Complexity and Helical Inversion in Supramolecular Assemblies Through Solvent‐Induced Radical Disparities |
| title_full | Revealing Pathway Complexity and Helical Inversion in Supramolecular Assemblies Through Solvent‐Induced Radical Disparities |
| title_fullStr | Revealing Pathway Complexity and Helical Inversion in Supramolecular Assemblies Through Solvent‐Induced Radical Disparities |
| title_full_unstemmed | Revealing Pathway Complexity and Helical Inversion in Supramolecular Assemblies Through Solvent‐Induced Radical Disparities |
| title_short | Revealing Pathway Complexity and Helical Inversion in Supramolecular Assemblies Through Solvent‐Induced Radical Disparities |
| title_sort | revealing pathway complexity and helical inversion in supramolecular assemblies through solvent induced radical disparities |
| topic | helical inversion pathway complexity radicals solvent–solute interaction supramolecular assembly |
| url | https://doi.org/10.1002/advs.202308371 |
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