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Solvent-controlled E/Z isomerization vs. [2 + 2] photocycloaddition mediated by supramolecular polymerization
Control over the photochemical outcome of photochromic molecules in solution represents a major challenge, as photoexcitation often leads to multiple competing photochemical and/or supramolecular pathways resulting in complex product mixtures. Herein, we demonstrate precise and efficient control ove...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8162386/ https://www.ncbi.nlm.nih.gov/pubmed/34094301 http://dx.doi.org/10.1039/d0sc03442h |
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author | Dünnebacke, Torsten Kartha, Kalathil K. Wahl, Johannes M. Albuquerque, Rodrigo Q. Fernández, Gustavo |
author_facet | Dünnebacke, Torsten Kartha, Kalathil K. Wahl, Johannes M. Albuquerque, Rodrigo Q. Fernández, Gustavo |
author_sort | Dünnebacke, Torsten |
collection | PubMed |
description | Control over the photochemical outcome of photochromic molecules in solution represents a major challenge, as photoexcitation often leads to multiple competing photochemical and/or supramolecular pathways resulting in complex product mixtures. Herein, we demonstrate precise and efficient control over the photochemical behaviour of cyanostilbenes in solution using a straightforward solvent-controlled approach based on supramolecular polymerization. To this end, we designed a π-extended cyanostilbene bolaamphiphile that exhibits tuneable solvent-dependent photochemical behaviour. Photoirradiation of the system in a monomeric state (in organic solvents) exclusively leads to a highly reversible and efficient E/Z photoisomerization, whereas a nearly quantitative [2 + 2] photocycloaddition into a single cyclobutane (anti head-to-tail) occurs in aqueous solutions. These results can be rationalized by a highly regular and preorganized antiparallel J-type arrangement of the cyanostilbene units that is driven by aqueous supramolecular polymerization. The presented concept demonstrates a novel approach towards solvent-selective and environmentally friendly photochemical transformations, which is expected to broaden the scope of supramolecular polymerization. |
format | Online Article Text |
id | pubmed-8162386 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81623862021-06-04 Solvent-controlled E/Z isomerization vs. [2 + 2] photocycloaddition mediated by supramolecular polymerization Dünnebacke, Torsten Kartha, Kalathil K. Wahl, Johannes M. Albuquerque, Rodrigo Q. Fernández, Gustavo Chem Sci Chemistry Control over the photochemical outcome of photochromic molecules in solution represents a major challenge, as photoexcitation often leads to multiple competing photochemical and/or supramolecular pathways resulting in complex product mixtures. Herein, we demonstrate precise and efficient control over the photochemical behaviour of cyanostilbenes in solution using a straightforward solvent-controlled approach based on supramolecular polymerization. To this end, we designed a π-extended cyanostilbene bolaamphiphile that exhibits tuneable solvent-dependent photochemical behaviour. Photoirradiation of the system in a monomeric state (in organic solvents) exclusively leads to a highly reversible and efficient E/Z photoisomerization, whereas a nearly quantitative [2 + 2] photocycloaddition into a single cyclobutane (anti head-to-tail) occurs in aqueous solutions. These results can be rationalized by a highly regular and preorganized antiparallel J-type arrangement of the cyanostilbene units that is driven by aqueous supramolecular polymerization. The presented concept demonstrates a novel approach towards solvent-selective and environmentally friendly photochemical transformations, which is expected to broaden the scope of supramolecular polymerization. The Royal Society of Chemistry 2020-09-11 /pmc/articles/PMC8162386/ /pubmed/34094301 http://dx.doi.org/10.1039/d0sc03442h Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Dünnebacke, Torsten Kartha, Kalathil K. Wahl, Johannes M. Albuquerque, Rodrigo Q. Fernández, Gustavo Solvent-controlled E/Z isomerization vs. [2 + 2] photocycloaddition mediated by supramolecular polymerization |
title | Solvent-controlled E/Z isomerization vs. [2 + 2] photocycloaddition mediated by supramolecular polymerization |
title_full | Solvent-controlled E/Z isomerization vs. [2 + 2] photocycloaddition mediated by supramolecular polymerization |
title_fullStr | Solvent-controlled E/Z isomerization vs. [2 + 2] photocycloaddition mediated by supramolecular polymerization |
title_full_unstemmed | Solvent-controlled E/Z isomerization vs. [2 + 2] photocycloaddition mediated by supramolecular polymerization |
title_short | Solvent-controlled E/Z isomerization vs. [2 + 2] photocycloaddition mediated by supramolecular polymerization |
title_sort | solvent-controlled e/z isomerization vs. [2 + 2] photocycloaddition mediated by supramolecular polymerization |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8162386/ https://www.ncbi.nlm.nih.gov/pubmed/34094301 http://dx.doi.org/10.1039/d0sc03442h |
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