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Absolute configuration and host-guest binding of chiral porphyrin-cages by a combined chiroptical and theoretical approach
Porphyrin cage-compounds are used as biomimetic models and substrate-selective catalysts in supramolecular chemistry. In this work we present the resolution of planar-chiral porphyrin cages and the determination of their absolute configuration by vibrational circular dichroism in combination with de...
Autores principales: | , , , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7508876/ https://www.ncbi.nlm.nih.gov/pubmed/32963222 http://dx.doi.org/10.1038/s41467-020-18596-1 |
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author | Ouyang, Jiangkun Swartjes, Anne Geerts, Marc Gilissen, Pieter J. Wang, Danni Teeuwen, Paula C. P. Tinnemans, Paul Vanthuyne, Nicolas Chentouf, Sara Rutjes, Floris P. J. T. Naubron, Jean-Valère Crassous, Jeanne Elemans, Johannes A. A. W. Nolte, Roeland J. M. |
author_facet | Ouyang, Jiangkun Swartjes, Anne Geerts, Marc Gilissen, Pieter J. Wang, Danni Teeuwen, Paula C. P. Tinnemans, Paul Vanthuyne, Nicolas Chentouf, Sara Rutjes, Floris P. J. T. Naubron, Jean-Valère Crassous, Jeanne Elemans, Johannes A. A. W. Nolte, Roeland J. M. |
author_sort | Ouyang, Jiangkun |
collection | PubMed |
description | Porphyrin cage-compounds are used as biomimetic models and substrate-selective catalysts in supramolecular chemistry. In this work we present the resolution of planar-chiral porphyrin cages and the determination of their absolute configuration by vibrational circular dichroism in combination with density functional theory calculations. The chiral porphyrin-cages form complexes with achiral and chiral viologen-guests and upon binding one of the axial enantiomorphs of the guest is bound selectively, as is indicated by induced-electronic-dichroism-spectra in combination with calculations. This host-guest binding also leads to unusual enhanced vibrational circular dichroism, which is the result of a combination of phenomena, such as rigidification of the host and guest structures, charge transfer, and coupling of specific vibration modes of the host and guest. The results offer insights in how the porphyrin cage-compounds may be used to construct a future molecular Turing machine that can write chiral information onto polymer chains. |
format | Online Article Text |
id | pubmed-7508876 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-75088762020-10-08 Absolute configuration and host-guest binding of chiral porphyrin-cages by a combined chiroptical and theoretical approach Ouyang, Jiangkun Swartjes, Anne Geerts, Marc Gilissen, Pieter J. Wang, Danni Teeuwen, Paula C. P. Tinnemans, Paul Vanthuyne, Nicolas Chentouf, Sara Rutjes, Floris P. J. T. Naubron, Jean-Valère Crassous, Jeanne Elemans, Johannes A. A. W. Nolte, Roeland J. M. Nat Commun Article Porphyrin cage-compounds are used as biomimetic models and substrate-selective catalysts in supramolecular chemistry. In this work we present the resolution of planar-chiral porphyrin cages and the determination of their absolute configuration by vibrational circular dichroism in combination with density functional theory calculations. The chiral porphyrin-cages form complexes with achiral and chiral viologen-guests and upon binding one of the axial enantiomorphs of the guest is bound selectively, as is indicated by induced-electronic-dichroism-spectra in combination with calculations. This host-guest binding also leads to unusual enhanced vibrational circular dichroism, which is the result of a combination of phenomena, such as rigidification of the host and guest structures, charge transfer, and coupling of specific vibration modes of the host and guest. The results offer insights in how the porphyrin cage-compounds may be used to construct a future molecular Turing machine that can write chiral information onto polymer chains. Nature Publishing Group UK 2020-09-22 /pmc/articles/PMC7508876/ /pubmed/32963222 http://dx.doi.org/10.1038/s41467-020-18596-1 Text en © The Author(s) 2020 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. |
spellingShingle | Article Ouyang, Jiangkun Swartjes, Anne Geerts, Marc Gilissen, Pieter J. Wang, Danni Teeuwen, Paula C. P. Tinnemans, Paul Vanthuyne, Nicolas Chentouf, Sara Rutjes, Floris P. J. T. Naubron, Jean-Valère Crassous, Jeanne Elemans, Johannes A. A. W. Nolte, Roeland J. M. Absolute configuration and host-guest binding of chiral porphyrin-cages by a combined chiroptical and theoretical approach |
title | Absolute configuration and host-guest binding of chiral porphyrin-cages by a combined chiroptical and theoretical approach |
title_full | Absolute configuration and host-guest binding of chiral porphyrin-cages by a combined chiroptical and theoretical approach |
title_fullStr | Absolute configuration and host-guest binding of chiral porphyrin-cages by a combined chiroptical and theoretical approach |
title_full_unstemmed | Absolute configuration and host-guest binding of chiral porphyrin-cages by a combined chiroptical and theoretical approach |
title_short | Absolute configuration and host-guest binding of chiral porphyrin-cages by a combined chiroptical and theoretical approach |
title_sort | absolute configuration and host-guest binding of chiral porphyrin-cages by a combined chiroptical and theoretical approach |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7508876/ https://www.ncbi.nlm.nih.gov/pubmed/32963222 http://dx.doi.org/10.1038/s41467-020-18596-1 |
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