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Influence of Ag(+) on the Magnetic Response of [2.2.2]Paracyclophane: NMR Properties of a Prototypical Organic Host for Cation Binding Based on DFT Calculations
The complexation of metal cations into a host–guest situation is particularly well exemplified by [2.2.2]paracyclophane and Ag(I), which leads to a strong cation–π interaction with a specific face of the host molecule. Through this study we sought a deeper understanding of the effects the metal cent...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley & Sons, Ltd
2015
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4608534/ https://www.ncbi.nlm.nih.gov/pubmed/26491646 http://dx.doi.org/10.1002/open.201500106 |
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author | MacLeod Carey, Desmond Gomez, Tatiana Morales-Verdejo, Cesar Muñoz-Castro, Alvaro |
author_facet | MacLeod Carey, Desmond Gomez, Tatiana Morales-Verdejo, Cesar Muñoz-Castro, Alvaro |
author_sort | MacLeod Carey, Desmond |
collection | PubMed |
description | The complexation of metal cations into a host–guest situation is particularly well exemplified by [2.2.2]paracyclophane and Ag(I), which leads to a strong cation–π interaction with a specific face of the host molecule. Through this study we sought a deeper understanding of the effects the metal center has on the NMR spectroscopic properties of the prototypical organic host, generating theoretical reasons for the observed experimental results with an aim to determine the role of the cation–π interaction in a host–guest scenario. From an analysis of certain components of the induced magnetic field and the (13)C NMR shielding tensor under its own principal axis system (PAS), the local and overall magnetic behavior can be clearly described. Interestingly, the magnetic response of such a complex exhibits a large axis-dependent behavior, which leads to an overall shielding effect for the coordinating carbon atoms and a deshielding effect for the respective uncoordinated counterparts, evidence that complements previous experimental results. This proposed approach can be useful to gain further insight into the local and overall variation of NMR shifts for host–guest pairs involving both inorganic and organic hosts. |
format | Online Article Text |
id | pubmed-4608534 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2015 |
publisher | John Wiley & Sons, Ltd |
record_format | MEDLINE/PubMed |
spelling | pubmed-46085342015-10-21 Influence of Ag(+) on the Magnetic Response of [2.2.2]Paracyclophane: NMR Properties of a Prototypical Organic Host for Cation Binding Based on DFT Calculations MacLeod Carey, Desmond Gomez, Tatiana Morales-Verdejo, Cesar Muñoz-Castro, Alvaro ChemistryOpen Full Papers The complexation of metal cations into a host–guest situation is particularly well exemplified by [2.2.2]paracyclophane and Ag(I), which leads to a strong cation–π interaction with a specific face of the host molecule. Through this study we sought a deeper understanding of the effects the metal center has on the NMR spectroscopic properties of the prototypical organic host, generating theoretical reasons for the observed experimental results with an aim to determine the role of the cation–π interaction in a host–guest scenario. From an analysis of certain components of the induced magnetic field and the (13)C NMR shielding tensor under its own principal axis system (PAS), the local and overall magnetic behavior can be clearly described. Interestingly, the magnetic response of such a complex exhibits a large axis-dependent behavior, which leads to an overall shielding effect for the coordinating carbon atoms and a deshielding effect for the respective uncoordinated counterparts, evidence that complements previous experimental results. This proposed approach can be useful to gain further insight into the local and overall variation of NMR shifts for host–guest pairs involving both inorganic and organic hosts. John Wiley & Sons, Ltd 2015-10 2015-06-26 /pmc/articles/PMC4608534/ /pubmed/26491646 http://dx.doi.org/10.1002/open.201500106 Text en © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. http://creativecommons.org/licenses/by-nc-nd/4.0/ This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made. |
spellingShingle | Full Papers MacLeod Carey, Desmond Gomez, Tatiana Morales-Verdejo, Cesar Muñoz-Castro, Alvaro Influence of Ag(+) on the Magnetic Response of [2.2.2]Paracyclophane: NMR Properties of a Prototypical Organic Host for Cation Binding Based on DFT Calculations |
title | Influence of Ag(+) on the Magnetic Response of [2.2.2]Paracyclophane: NMR Properties of a Prototypical Organic Host for Cation Binding Based on DFT Calculations |
title_full | Influence of Ag(+) on the Magnetic Response of [2.2.2]Paracyclophane: NMR Properties of a Prototypical Organic Host for Cation Binding Based on DFT Calculations |
title_fullStr | Influence of Ag(+) on the Magnetic Response of [2.2.2]Paracyclophane: NMR Properties of a Prototypical Organic Host for Cation Binding Based on DFT Calculations |
title_full_unstemmed | Influence of Ag(+) on the Magnetic Response of [2.2.2]Paracyclophane: NMR Properties of a Prototypical Organic Host for Cation Binding Based on DFT Calculations |
title_short | Influence of Ag(+) on the Magnetic Response of [2.2.2]Paracyclophane: NMR Properties of a Prototypical Organic Host for Cation Binding Based on DFT Calculations |
title_sort | influence of ag(+) on the magnetic response of [2.2.2]paracyclophane: nmr properties of a prototypical organic host for cation binding based on dft calculations |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4608534/ https://www.ncbi.nlm.nih.gov/pubmed/26491646 http://dx.doi.org/10.1002/open.201500106 |
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