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Synthesis and properties of open fullerenes encapsulating ammonia and methane

Synthesis and properties of open fullerenes encapsulating ammonia and methane
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 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 NH31, 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.
fullerenes
1439-4235
266-276
Bloodworth, Sally
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Gravisk, John
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Alom, Shamim
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Kouril, Karel
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Elliott, Stuart
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Wells, Neil J.
86312185-007b-495b-86da-4e2e5b9b8025
Horsewill, Anthony J.
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Mamone, Salvatore
a36f5468-abcb-47d8-9bff-0dddec553a5e
Jiménez-Ruiz, Mónica
5563c1b2-5b37-43cf-ac34-6d734c125eec
Rols, Stéphane
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Nagel, Urmas
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Rõõm, Toomas
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Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b
Bloodworth, Sally
943160fc-1b70-4c29-b2e3-b7785cee8a0c
Gravisk, John
28699f13-0e49-49f5-b1e6-540f342096b3
Alom, Shamim
f6b56fb1-7f94-432a-87cd-887f6e5d9f64
Kouril, Karel
75bde80c-90bd-49c4-8b89-ec1a7b39363a
Elliott, Stuart
6cc724de-f75f-4c0f-a00a-e712b4e73b12
Wells, Neil J.
86312185-007b-495b-86da-4e2e5b9b8025
Horsewill, Anthony J.
262eff25-a868-4984-83a6-f2a5090e7635
Mamone, Salvatore
a36f5468-abcb-47d8-9bff-0dddec553a5e
Jiménez-Ruiz, Mónica
5563c1b2-5b37-43cf-ac34-6d734c125eec
Rols, Stéphane
604c9299-aeff-4d5e-a16c-54a2f9b50108
Nagel, Urmas
18190a5a-a4c2-49d2-9a44-2ba31eb57655
Rõõm, Toomas
49325730-0d65-4f8a-b8b8-776696939cbc
Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b

Bloodworth, Sally, Gravisk, John, Alom, Shamim, Kouril, Karel, Elliott, Stuart, Wells, Neil J., Horsewill, Anthony J., Mamone, Salvatore, Jiménez-Ruiz, Mónica, Rols, Stéphane, Nagel, Urmas, Rõõm, Toomas, Levitt, Malcolm H. and Whitby, Richard J. (2018) Synthesis and properties of open fullerenes encapsulating ammonia and methane. Chemphyschem, 19, 266-276. (doi:10.1002/cphc.201701212).

Record type: Article

Abstract

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 NH31, 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.

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Accepted/In Press date: 9 November 2017
e-pub ahead of print date: 13 November 2017
Published date: 4 January 2018
Keywords: fullerenes

Identifiers

Local EPrints ID: 415723
URI: https://eprints.soton.ac.uk/id/eprint/415723
ISSN: 1439-4235
PURE UUID: ab71704d-6379-4a4e-88f1-3f1e709bd1e2
ORCID for Sally Bloodworth: ORCID iD orcid.org/0000-0003-2219-3635
ORCID for Karel Kouril: ORCID iD orcid.org/0000-0003-4884-1637
ORCID for Neil J. Wells: ORCID iD orcid.org/0000-0002-4607-5791
ORCID for Malcolm H. Levitt: ORCID iD orcid.org/0000-0001-9878-1180
ORCID for Richard J. Whitby: ORCID iD orcid.org/0000-0002-9891-5502

Catalogue record

Date deposited: 21 Nov 2017 17:30
Last modified: 13 Nov 2018 05:01

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Contributors

Author: John Gravisk
Author: Shamim Alom
Author: Karel Kouril ORCID iD
Author: Stuart Elliott
Author: Neil J. Wells ORCID iD
Author: Anthony J. Horsewill
Author: Salvatore Mamone
Author: Mónica Jiménez-Ruiz
Author: Stéphane Rols
Author: Urmas Nagel
Author: Toomas Rõõm

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