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Distance Matters: Biasing Mechanism, Transfer of Asymmetry, and Stereomutation in N-Annulated Perylene Bisimide Supramolecular Polymers
[Image: see text] The synthesis of two series of N-annulated perylene bisimides (PBIs), compounds 1 and 2, is reported, and their self-assembling features are thoroughly investigated by a complete set of spectroscopic measurements and theoretical calculations. The study corroborates the enormous inf...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2021
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8478275/ https://www.ncbi.nlm.nih.gov/pubmed/34378925 http://dx.doi.org/10.1021/jacs.1c06125 |
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author | Martínez, Manuel A. Doncel-Giménez, Azahara Cerdá, Jesús Calbo, Joaquín Rodríguez, Rafael Aragó, Juan Crassous, Jeanne Ortí, Enrique Sánchez, Luis |
author_facet | Martínez, Manuel A. Doncel-Giménez, Azahara Cerdá, Jesús Calbo, Joaquín Rodríguez, Rafael Aragó, Juan Crassous, Jeanne Ortí, Enrique Sánchez, Luis |
author_sort | Martínez, Manuel A. |
collection | PubMed |
description | [Image: see text] The synthesis of two series of N-annulated perylene bisimides (PBIs), compounds 1 and 2, is reported, and their self-assembling features are thoroughly investigated by a complete set of spectroscopic measurements and theoretical calculations. The study corroborates the enormous influence that the distance between the PBI core and the peripheral groups exerts on the chiroptical properties and the supramolecular polymerization mechanism. Compounds 1, with the peripheral groups separated from the central PBI core by two methylenes and an ester group, form J-type supramolecular polymers in a cooperative manner but exhibit negligible chiroptical properties. The lack of clear helicity, due to the staircase arrangement of the self-assembling units in the aggregate, justifies these features. In contrast, attaching the peripheral groups directly to the N-annulated PBI core drastically changes the self-assembling properties of compounds 2, which form H-type aggregates following an isodesmic mechanism. These H-type aggregates show a strong aggregation-caused quenching (ACQ) effect that leads to nonemissive aggregates. Chiral (S)-2 and (R)-2 experience an efficient transfer of asymmetry to afford P- and M-type aggregates, respectively, although no amplification of asymmetry is achieved in majority rules or “sergeants-and-soldiers” experiments. A solvent-controlled stereomutation is observed for chiral (S)-2 and (R)-2, which form helical supramolecular polymers of different handedness depending on the solvent (methylcyclohexane or toluene). The stereomutation is accounted for by considering the two possible conformations of the terminal phenyl groups, eclipsed or staggered, which lead to linear or helical self-assemblies, respectively, with different relative stabilities depending on the solvent. |
format | Online Article Text |
id | pubmed-8478275 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-84782752021-09-29 Distance Matters: Biasing Mechanism, Transfer of Asymmetry, and Stereomutation in N-Annulated Perylene Bisimide Supramolecular Polymers Martínez, Manuel A. Doncel-Giménez, Azahara Cerdá, Jesús Calbo, Joaquín Rodríguez, Rafael Aragó, Juan Crassous, Jeanne Ortí, Enrique Sánchez, Luis J Am Chem Soc [Image: see text] The synthesis of two series of N-annulated perylene bisimides (PBIs), compounds 1 and 2, is reported, and their self-assembling features are thoroughly investigated by a complete set of spectroscopic measurements and theoretical calculations. The study corroborates the enormous influence that the distance between the PBI core and the peripheral groups exerts on the chiroptical properties and the supramolecular polymerization mechanism. Compounds 1, with the peripheral groups separated from the central PBI core by two methylenes and an ester group, form J-type supramolecular polymers in a cooperative manner but exhibit negligible chiroptical properties. The lack of clear helicity, due to the staircase arrangement of the self-assembling units in the aggregate, justifies these features. In contrast, attaching the peripheral groups directly to the N-annulated PBI core drastically changes the self-assembling properties of compounds 2, which form H-type aggregates following an isodesmic mechanism. These H-type aggregates show a strong aggregation-caused quenching (ACQ) effect that leads to nonemissive aggregates. Chiral (S)-2 and (R)-2 experience an efficient transfer of asymmetry to afford P- and M-type aggregates, respectively, although no amplification of asymmetry is achieved in majority rules or “sergeants-and-soldiers” experiments. A solvent-controlled stereomutation is observed for chiral (S)-2 and (R)-2, which form helical supramolecular polymers of different handedness depending on the solvent (methylcyclohexane or toluene). The stereomutation is accounted for by considering the two possible conformations of the terminal phenyl groups, eclipsed or staggered, which lead to linear or helical self-assemblies, respectively, with different relative stabilities depending on the solvent. American Chemical Society 2021-08-11 2021-08-25 /pmc/articles/PMC8478275/ /pubmed/34378925 http://dx.doi.org/10.1021/jacs.1c06125 Text en © 2021 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 | Martínez, Manuel A. Doncel-Giménez, Azahara Cerdá, Jesús Calbo, Joaquín Rodríguez, Rafael Aragó, Juan Crassous, Jeanne Ortí, Enrique Sánchez, Luis Distance Matters: Biasing Mechanism, Transfer of Asymmetry, and Stereomutation in N-Annulated Perylene Bisimide Supramolecular Polymers |
title | Distance
Matters: Biasing Mechanism, Transfer of Asymmetry,
and Stereomutation in N-Annulated Perylene Bisimide Supramolecular
Polymers |
title_full | Distance
Matters: Biasing Mechanism, Transfer of Asymmetry,
and Stereomutation in N-Annulated Perylene Bisimide Supramolecular
Polymers |
title_fullStr | Distance
Matters: Biasing Mechanism, Transfer of Asymmetry,
and Stereomutation in N-Annulated Perylene Bisimide Supramolecular
Polymers |
title_full_unstemmed | Distance
Matters: Biasing Mechanism, Transfer of Asymmetry,
and Stereomutation in N-Annulated Perylene Bisimide Supramolecular
Polymers |
title_short | Distance
Matters: Biasing Mechanism, Transfer of Asymmetry,
and Stereomutation in N-Annulated Perylene Bisimide Supramolecular
Polymers |
title_sort | distance
matters: biasing mechanism, transfer of asymmetry,
and stereomutation in n-annulated perylene bisimide supramolecular
polymers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8478275/ https://www.ncbi.nlm.nih.gov/pubmed/34378925 http://dx.doi.org/10.1021/jacs.1c06125 |
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