Chemical shielding of H2O and HF encapsulated inside a C60 cage

Samuel P. Jarvis; Hongqian Sang; Filipe Junqueira; Oliver Gordon; Jo E.A. Hodgkinson; Alex Saywell; Philipp Rahe; Salvatore Mamone; Simon Taylor; Adam Sweetman; Jeremy Leaf; David A. Duncan; Tien Lin Lee; Pardeep K. Thakur; Gabriella Hoffman; Richard J. Whitby; Malcolm H. Levitt; Georg Held; Lev Kantorovich; Philip Moriarty; Robert G. Jones

doi:10.1038/s42004-021-00569-0

Chemical shielding of H₂O and HF encapsulated inside a C₆₀ cage

Samuel P. Jarvis^*, Hongqian Sang, Filipe Junqueira, Oliver Gordon, Jo E.A. Hodgkinson, Alex Saywell, Philipp Rahe, Salvatore Mamone, Simon Taylor, Adam Sweetman, Jeremy Leaf, David A. Duncan, Tien Lin Lee, Pardeep K. Thakur, Gabriella Hoffman, Richard J. Whitby, Malcolm H. Levitt, Georg Held, Lev Kantorovich, Philip MoriartyRobert G. Jones

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

13 Citations (Scopus)

Abstract

Molecular surgery provides the opportunity to study relatively large molecules encapsulated within a fullerene cage. Here we determine the location of an H₂O 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 H₂O 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 H₂O 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.

Original language	English
Article number	135
Journal	Communications Chemistry
Volume	4
Issue number	1
DOIs	https://doi.org/10.1038/s42004-021-00569-0
Publication status	Published - Dec 2021

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Jarvis, S. P., Sang, H., Junqueira, F., Gordon, O., Hodgkinson, J. E. A., Saywell, A., Rahe, P., Mamone, S., Taylor, S., Sweetman, A., Leaf, J., Duncan, D. A., Lee, T. L., Thakur, P. K., Hoffman, G., Whitby, R. J., Levitt, M. H., Held, G., Kantorovich, L., ... Jones, R. G. (2021). Chemical shielding of H₂O and HF encapsulated inside a C₆₀ cage. Communications Chemistry, 4(1), Article 135. https://doi.org/10.1038/s42004-021-00569-0

@article{75586788d7d44e95ba33226c2e9834d3,

title = "Chemical shielding of H2O and HF encapsulated inside a C60 cage",

abstract = "Molecular surgery provides the opportunity to study relatively large molecules encapsulated within a fullerene cage. Here we determine the location of an H2O 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 H2O 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 H2O 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.",

author = "Jarvis, {Samuel P.} and Hongqian Sang and Filipe Junqueira and Oliver Gordon and Hodgkinson, {Jo E.A.} and Alex Saywell and Philipp Rahe and Salvatore Mamone and Simon Taylor and Adam Sweetman and Jeremy Leaf and Duncan, {David A.} and Lee, {Tien Lin} and Thakur, {Pardeep K.} and Gabriella Hoffman and Whitby, {Richard J.} and Levitt, {Malcolm H.} and Georg Held and Lev Kantorovich and Philip Moriarty and Jones, {Robert G.}",

note = "Funding Information: We thank Diamond Light Source for the award of beam times SI12979, SI15022, and SI23644. S.P.J. thanks the Engineering and Physical Sciences Research Council (EPSRC), the Royal Society, and the Leverhulme Trust, respectively, for grants EP/V00767X/1, PI70026, and ECF-2015-005. P.J.M. gratefully acknowledges funding via an EPSRC Established Career Fellowship (EP/T033568/1). A.S. and P.R. acknowledge funding from the People Programme (Marie Curie Actions) of the European Union{\textquoteright}s Seventh Framework Programme for grants 623992 and 628439, respectively. A.S. also acknowledges support via a Royal Society University Research Fellowship. M.H.L. acknowledges EPSRC funding grants EP/P009980/1 and EP/T004320/1. Publisher Copyright: {\textcopyright} 2021, The Author(s). Copyright: Copyright 2021 Elsevier B.V., All rights reserved.",

year = "2021",

month = dec,

doi = "10.1038/s42004-021-00569-0",

language = "English",

volume = "4",

journal = "Communications Chemistry",

issn = "2399-3669",

publisher = "Springer Nature",

number = "1",

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Jarvis, SP, Sang, H, Junqueira, F, Gordon, O, Hodgkinson, JEA, Saywell, A, Rahe, P, Mamone, S, Taylor, S, Sweetman, A, Leaf, J, Duncan, DA, Lee, TL, Thakur, PK, Hoffman, G, Whitby, RJ, Levitt, MH, Held, G, Kantorovich, L, Moriarty, P & Jones, RG 2021, 'Chemical shielding of H₂O and HF encapsulated inside a C₆₀ cage', Communications Chemistry, vol. 4, no. 1, 135. https://doi.org/10.1038/s42004-021-00569-0

TY - JOUR

T1 - Chemical shielding of H2O and HF encapsulated inside a C60 cage

AU - Jarvis, Samuel P.

AU - Sang, Hongqian

AU - Junqueira, Filipe

AU - Gordon, Oliver

AU - Hodgkinson, Jo E.A.

AU - Saywell, Alex

AU - Rahe, Philipp

AU - Mamone, Salvatore

AU - Taylor, Simon

AU - Sweetman, Adam

AU - Leaf, Jeremy

AU - Duncan, David A.

AU - Lee, Tien Lin

AU - Thakur, Pardeep K.

AU - Hoffman, Gabriella

AU - Whitby, Richard J.

AU - Levitt, Malcolm H.

AU - Held, Georg

AU - Kantorovich, Lev

AU - Moriarty, Philip

AU - Jones, Robert G.

N1 - Funding Information: We thank Diamond Light Source for the award of beam times SI12979, SI15022, and SI23644. S.P.J. thanks the Engineering and Physical Sciences Research Council (EPSRC), the Royal Society, and the Leverhulme Trust, respectively, for grants EP/V00767X/1, PI70026, and ECF-2015-005. P.J.M. gratefully acknowledges funding via an EPSRC Established Career Fellowship (EP/T033568/1). A.S. and P.R. acknowledge funding from the People Programme (Marie Curie Actions) of the European Union’s Seventh Framework Programme for grants 623992 and 628439, respectively. A.S. also acknowledges support via a Royal Society University Research Fellowship. M.H.L. acknowledges EPSRC funding grants EP/P009980/1 and EP/T004320/1. Publisher Copyright: © 2021, The Author(s). Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/12

Y1 - 2021/12

N2 - Molecular surgery provides the opportunity to study relatively large molecules encapsulated within a fullerene cage. Here we determine the location of an H2O 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 H2O 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 H2O 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.

AB - Molecular surgery provides the opportunity to study relatively large molecules encapsulated within a fullerene cage. Here we determine the location of an H2O 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 H2O 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 H2O 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.

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U2 - 10.1038/s42004-021-00569-0

DO - 10.1038/s42004-021-00569-0

M3 - Article

AN - SCOPUS:85115429246

SN - 2399-3669

VL - 4

JO - Communications Chemistry

JF - Communications Chemistry

IS - 1

M1 - 135

ER -

Chemical shielding of H₂O and HF encapsulated inside a C₆₀ cage

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