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Chemical shielding of H(2)O and HF encapsulated inside a C(60) cage
Molecular surgery provides the opportunity to study relatively large molecules encapsulated within a fullerene cage. Here we determine the location of an H(2)O molecule isolated within an adsorbed buckminsterfullerene cage, and compare this to the intrafullerene position of HF. Using normal incidenc...
Autores principales: | , , , , , , , , , , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814403/ https://www.ncbi.nlm.nih.gov/pubmed/36697850 http://dx.doi.org/10.1038/s42004-021-00569-0 |
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author | Jarvis, Samuel P. Sang, Hongqian Junqueira, Filipe Gordon, Oliver Hodgkinson, Jo E. A. Saywell, Alex Rahe, Philipp Mamone, Salvatore Taylor, Simon Sweetman, Adam Leaf, Jeremy Duncan, David A. Lee, Tien-Lin Thakur, Pardeep K. Hoffman, Gabriella Whitby, Richard J. Levitt, Malcolm H. Held, Georg Kantorovich, Lev Moriarty, Philip Jones, Robert G. |
author_facet | Jarvis, Samuel P. Sang, Hongqian Junqueira, Filipe Gordon, Oliver Hodgkinson, Jo E. A. Saywell, Alex Rahe, Philipp Mamone, Salvatore Taylor, Simon Sweetman, Adam Leaf, Jeremy Duncan, David A. Lee, Tien-Lin Thakur, Pardeep K. Hoffman, Gabriella Whitby, Richard J. Levitt, Malcolm H. Held, Georg Kantorovich, Lev Moriarty, Philip Jones, Robert G. |
author_sort | Jarvis, Samuel P. |
collection | PubMed |
description | Molecular surgery provides the opportunity to study relatively large molecules encapsulated within a fullerene cage. Here we determine the location of an H(2)O molecule isolated within an adsorbed buckminsterfullerene cage, and compare this to the intrafullerene position of HF. Using normal incidence X-ray standing wave (NIXSW) analysis, coupled with density functional theory and molecular dynamics simulations, we show that both H(2)O and HF are located at an off-centre position within the fullerene cage, caused by substantial intra-cage electrostatic fields generated by surface adsorption of the fullerene. The atomistic and electronic structure simulations also reveal significant internal rotational motion consistent with the NIXSW data. Despite this substantial intra-cage interaction, we find that neither HF or H(2)O contribute to the endofullerene frontier orbitals, confirming the chemical isolation of the encapsulated molecules. We also show that our experimental NIXSW measurements and theoretical data are best described by a mixed adsorption site model. |
format | Online Article Text |
id | pubmed-9814403 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-98144032023-01-10 Chemical shielding of H(2)O and HF encapsulated inside a C(60) cage Jarvis, Samuel P. Sang, Hongqian Junqueira, Filipe Gordon, Oliver Hodgkinson, Jo E. A. Saywell, Alex Rahe, Philipp Mamone, Salvatore Taylor, Simon Sweetman, Adam Leaf, Jeremy Duncan, David A. Lee, Tien-Lin Thakur, Pardeep K. Hoffman, Gabriella Whitby, Richard J. Levitt, Malcolm H. Held, Georg Kantorovich, Lev Moriarty, Philip Jones, Robert G. Commun Chem Article Molecular surgery provides the opportunity to study relatively large molecules encapsulated within a fullerene cage. Here we determine the location of an H(2)O molecule isolated within an adsorbed buckminsterfullerene cage, and compare this to the intrafullerene position of HF. Using normal incidence X-ray standing wave (NIXSW) analysis, coupled with density functional theory and molecular dynamics simulations, we show that both H(2)O and HF are located at an off-centre position within the fullerene cage, caused by substantial intra-cage electrostatic fields generated by surface adsorption of the fullerene. The atomistic and electronic structure simulations also reveal significant internal rotational motion consistent with the NIXSW data. Despite this substantial intra-cage interaction, we find that neither HF or H(2)O contribute to the endofullerene frontier orbitals, confirming the chemical isolation of the encapsulated molecules. We also show that our experimental NIXSW measurements and theoretical data are best described by a mixed adsorption site model. Nature Publishing Group UK 2021-09-22 /pmc/articles/PMC9814403/ /pubmed/36697850 http://dx.doi.org/10.1038/s42004-021-00569-0 Text en © The Author(s) 2021 https://creativecommons.org/licenses/by/4.0/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/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Jarvis, Samuel P. Sang, Hongqian Junqueira, Filipe Gordon, Oliver Hodgkinson, Jo E. A. Saywell, Alex Rahe, Philipp Mamone, Salvatore Taylor, Simon Sweetman, Adam Leaf, Jeremy Duncan, David A. Lee, Tien-Lin Thakur, Pardeep K. Hoffman, Gabriella Whitby, Richard J. Levitt, Malcolm H. Held, Georg Kantorovich, Lev Moriarty, Philip Jones, Robert G. Chemical shielding of H(2)O and HF encapsulated inside a C(60) cage |
title | Chemical shielding of H(2)O and HF encapsulated inside a C(60) cage |
title_full | Chemical shielding of H(2)O and HF encapsulated inside a C(60) cage |
title_fullStr | Chemical shielding of H(2)O and HF encapsulated inside a C(60) cage |
title_full_unstemmed | Chemical shielding of H(2)O and HF encapsulated inside a C(60) cage |
title_short | Chemical shielding of H(2)O and HF encapsulated inside a C(60) cage |
title_sort | chemical shielding of h(2)o and hf encapsulated inside a c(60) cage |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814403/ https://www.ncbi.nlm.nih.gov/pubmed/36697850 http://dx.doi.org/10.1038/s42004-021-00569-0 |
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