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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...

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Autores principales: MacLeod Carey, Desmond, Gomez, Tatiana, Morales-Verdejo, Cesar, Muñoz-Castro, Alvaro
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley & Sons, Ltd 2015
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.
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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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