Chemical shielding of H2O and HF encapsulated inside a C60 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.

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.

Citation

Jarvis, S. P., Sang, H., Junqueira, F., Gordon, O., Hodgkinson, J. E. A., Saywell, A., …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

• Journal Article Type: Article
• Acceptance Date: Aug 24, 2021
• Online Publication Date: Sep 22, 2021
• Publication Date: Sep 22, 2021
• Deposit Date: Oct 22, 2021
• Publicly Available Date: Oct 22, 2021
• Journal: Communications Chemistry
• Print ISSN: 2399-3669
• Electronic ISSN: 2399-3669
• Publisher: Springer Science and Business Media LLC
• Peer Reviewed: Peer Reviewed
• Volume: 4
• Issue: 1
• Article Number: 135
• DOI: https://doi.org/10.1038/s42004-021-00569-0
• Keywords: Materials Chemistry; Biochemistry; Environmental Chemistry; General Chemistry
• Public URL: https://nottingham-repository.worktribe.com/output/6508635
• Publisher URL: https://www.nature.com/articles/s42004-021-00569-0