Synthesis and properties of open fullerenes encapsulating ammonia and methane
We describe the synthesis and characterisation of open fullerene (1) and its reduced form (2) in which CH₄ and NH₃ are encapsulated, respectively. The ¹H NMR resonance of endohedral NH₃ is broadened by scalar coupling to the quadrupolar ¹⁴N nucleus, which relaxes rapidly. This broadening is absent f...
| Main Authors: | , , , , , , , , , , , , , |
|---|---|
| Format: | Article |
| Published: |
Wiley
2018
|
| Subjects: | |
| Online Access: | https://eprints.nottingham.ac.uk/50033/ |
| _version_ | 1848798134726033408 |
|---|---|
| author | Bloodworth, Sally Gräsvik, John Alom, Shamim Kouril,, Karel Elliott, Stuart J. Wells, Neil J. Horsewill, Anthony J. Mamone, Salvatore Jimenez-Ruiz, Monica Rols, Stéphane Nagel, Urmas Room, Toomas Levitt, Malcolm H. Whitby, Richard J. |
| author_facet | Bloodworth, Sally Gräsvik, John Alom, Shamim Kouril,, Karel Elliott, Stuart J. Wells, Neil J. Horsewill, Anthony J. Mamone, Salvatore Jimenez-Ruiz, Monica Rols, Stéphane Nagel, Urmas Room, Toomas Levitt, Malcolm H. Whitby, Richard J. |
| author_sort | Bloodworth, Sally |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | We describe the synthesis and characterisation of open fullerene (1) and its reduced form (2) in which CH₄ and NH₃ are encapsulated, respectively. The ¹H NMR resonance of endohedral NH₃ is broadened by scalar coupling to the quadrupolar ¹⁴N nucleus, which relaxes rapidly. This broadening is absent for small satellite peaks, which are attributed to natural abundance ¹⁵N. The influence of the scalar relaxation mechanism on the linewidth of the ¹H ammonia resonance is probed by variable temperature NMR. A rotational correlation time of τc= 1.5 ps. is determined for endohedral NH₃, and of τc=57±5 ps. for the open fullerene, indicating free rotation of the encapsulated molecule. IR spectroscopy of NH3@2 at 5 K identifies three vibrations of NH₃ (ν₁, ν₃ and ν₄) redshifted in comparison with free NH₃, and temperature dependence of the IR peak intensity indicates the presence of a large number of excited translational/ rotational states. Variable temperature ¹H NMR spectra indicate that endohedral CH4 is also able to rotate freely at 223 K, on the NMR timescale. Inelastic neutron scattering (INS) spectra of CH₄@1 show both rotational and translational modes of CH₄. Energy of the first excited rotational state (J=1) of CH₄@1 is significantly lower than that of free CH₄. |
| first_indexed | 2025-11-14T20:14:57Z |
| format | Article |
| id | nottingham-50033 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T20:14:57Z |
| publishDate | 2018 |
| publisher | Wiley |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-500332020-05-04T19:30:50Z https://eprints.nottingham.ac.uk/50033/ Synthesis and properties of open fullerenes encapsulating ammonia and methane Bloodworth, Sally Gräsvik, John Alom, Shamim Kouril,, Karel Elliott, Stuart J. Wells, Neil J. Horsewill, Anthony J. Mamone, Salvatore Jimenez-Ruiz, Monica Rols, Stéphane Nagel, Urmas Room, Toomas Levitt, Malcolm H. Whitby, Richard J. We describe the synthesis and characterisation of open fullerene (1) and its reduced form (2) in which CH₄ and NH₃ are encapsulated, respectively. The ¹H NMR resonance of endohedral NH₃ is broadened by scalar coupling to the quadrupolar ¹⁴N nucleus, which relaxes rapidly. This broadening is absent for small satellite peaks, which are attributed to natural abundance ¹⁵N. The influence of the scalar relaxation mechanism on the linewidth of the ¹H ammonia resonance is probed by variable temperature NMR. A rotational correlation time of τc= 1.5 ps. is determined for endohedral NH₃, and of τc=57±5 ps. for the open fullerene, indicating free rotation of the encapsulated molecule. IR spectroscopy of NH3@2 at 5 K identifies three vibrations of NH₃ (ν₁, ν₃ and ν₄) redshifted in comparison with free NH₃, and temperature dependence of the IR peak intensity indicates the presence of a large number of excited translational/ rotational states. Variable temperature ¹H NMR spectra indicate that endohedral CH4 is also able to rotate freely at 223 K, on the NMR timescale. Inelastic neutron scattering (INS) spectra of CH₄@1 show both rotational and translational modes of CH₄. Energy of the first excited rotational state (J=1) of CH₄@1 is significantly lower than that of free CH₄. Wiley 2018-02-05 Article PeerReviewed Bloodworth, Sally, Gräsvik, John, Alom, Shamim, Kouril,, Karel, Elliott, Stuart J., Wells, Neil J., Horsewill, Anthony J., Mamone, Salvatore, Jimenez-Ruiz, Monica, Rols, Stéphane, Nagel, Urmas, Room, Toomas, Levitt, Malcolm H. and Whitby, Richard J. (2018) Synthesis and properties of open fullerenes encapsulating ammonia and methane. ChemPhysChem, 19 (3). pp. 266-276. ISSN 1439-7641 endofullerenes; inelastic neutron scattering spectroscopy; infra-red spectroscopy; NMR spectroscopy; SpinDynamica http://onlinelibrary.wiley.com/doi/10.1002/cphc.201701212/full doi:10.1002/cphc.201701212 doi:10.1002/cphc.201701212 |
| spellingShingle | endofullerenes; inelastic neutron scattering spectroscopy; infra-red spectroscopy; NMR spectroscopy; SpinDynamica Bloodworth, Sally Gräsvik, John Alom, Shamim Kouril,, Karel Elliott, Stuart J. Wells, Neil J. Horsewill, Anthony J. Mamone, Salvatore Jimenez-Ruiz, Monica Rols, Stéphane Nagel, Urmas Room, Toomas Levitt, Malcolm H. Whitby, Richard J. Synthesis and properties of open fullerenes encapsulating ammonia and methane |
| title | Synthesis and properties of open fullerenes encapsulating
ammonia and methane |
| title_full | Synthesis and properties of open fullerenes encapsulating
ammonia and methane |
| title_fullStr | Synthesis and properties of open fullerenes encapsulating
ammonia and methane |
| title_full_unstemmed | Synthesis and properties of open fullerenes encapsulating
ammonia and methane |
| title_short | Synthesis and properties of open fullerenes encapsulating
ammonia and methane |
| title_sort | synthesis and properties of open fullerenes encapsulating
ammonia and methane |
| topic | endofullerenes; inelastic neutron scattering spectroscopy; infra-red spectroscopy; NMR spectroscopy; SpinDynamica |
| url | https://eprints.nottingham.ac.uk/50033/ https://eprints.nottingham.ac.uk/50033/ https://eprints.nottingham.ac.uk/50033/ |