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Licence: CC BY: Creative Commons Attribution 4.0 International License
Research output: Contribution to Journal/Magazine › Journal article › peer-review
Chemical shielding of H2O and HF encapsulated inside a C60 cage. / Jarvis, Samuel; Sang, Hongqian; Junqueira, Filipe et al.
In: Communications Chemistry, Vol. 4, 135, 22.09.2021.Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - Chemical shielding of H2O and HF encapsulated inside a C60 cage
AU - Jarvis, Samuel
AU - Sang, Hongqian
AU - Junqueira, Filipe
AU - Gordon, Oliver
AU - Hodgkinson, Jo E
AU - Saywell, Alex
AU - Rahe, Philipp
AU - Mamone, Salvatore
AU - Taylor, Simon
AU - Sweetman, Adam
AU - Leaf, Jeremy
AU - Duncan, David
AU - Lee, Tien-Lin
AU - Thakur, Pardeep
AU - Hoffman, Gabriella
AU - Whitby, Richard
AU - Levitt, Malcolm
AU - Held, Georg
AU - Kantorovich, Lev
AU - Moriarty, Philip
AU - Jones, Robert
PY - 2021/9/22
Y1 - 2021/9/22
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.
U2 - 10.1038/s42004-021-00569-0
DO - 10.1038/s42004-021-00569-0
M3 - Journal article
VL - 4
JO - Communications Chemistry
JF - Communications Chemistry
SN - 2399-3669
M1 - 135
ER -