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First synthesis and characterization of CH4@C60

First synthesis and characterization of CH4@C60
First synthesis and characterization of CH4@C60
The endohedral fullerene CH4@C60, in which each C60 fullerene cage encapsulates a single methane molecule, has been synthesised for the first time. CH4 is the largest molecule, with the greatest number of atoms, to have been encapsulated in C60 to date. The key orifice contraction step, a photochemical desulfinylation of an open fullerene, was successfully completed, even though it is significantly inhibited by the presence of the endohedral molecule. The 13C NMR resonance for the cage nuclei in CH4@C60 is deshielded by Dd = +0.52 ppm relative to C60. The crystal structure of the nickel(II) octaethylporphyrin / benzene solvate shows no significant distortion of the carbon cage, relative to the C60 analogue, and shows the methane hydrogens as a shell of electron density around the central carbon, indicative of the quantum nature of the methane, existing in a set of quantised rotational-translational states at 100 K. The 1H and 13C spin-lattice relaxation times (T1) for endohedral methane have
been measured. The 1H T1 values are similar to those observed in the gas phase, also indicating that methane is freely rotating inside the C60 cage. The 1H relaxation rate constant T1 -1 increases with increasing temperature and suggests a significant spin-rotation contribution to the relaxation. The successful synthesis of CH4@C60 opens a route to endofullerenes incorporating larger guest molecules than those encapsulated previously.
endohedral fullerene, Mass spectrometry, NMR Spectroscopy, synthetic methods, X-ray diffraction
1433-7851
5038-5043
Bloodworth, Sally
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Sitinova, Gabriela
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Alom, Shamim
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Vidal, Sara
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Bacanu, George, Razvan
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Elliott, Stuart J
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Light, Mark
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Herniman, Julie
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Langley, G. John
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Levitt, Malcolm H.
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Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b
Bloodworth, Sally
943160fc-1b70-4c29-b2e3-b7785cee8a0c
Sitinova, Gabriela
8b98ba1c-ee09-4922-82e4-a9240aa12e64
Alom, Shamim
f6b56fb1-7f94-432a-87cd-887f6e5d9f64
Vidal, Sara
59c8a998-5646-44ff-82b7-1d3c556fbcc1
Bacanu, George, Razvan
181f3a56-e8da-445f-b9c6-c8ead171433f
Elliott, Stuart J
6cc724de-f75f-4c0f-a00a-e712b4e73b12
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
Herniman, Julie
530b1a36-1386-4602-8df7-defa6eb3512b
Langley, G. John
7ac80d61-b91d-4261-ad17-255f94ea21ea
Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b

Bloodworth, Sally, Sitinova, Gabriela, Alom, Shamim, Vidal, Sara, Bacanu, George, Razvan, Elliott, Stuart J, Light, Mark, Herniman, Julie, Langley, G. John, Levitt, Malcolm H. and Whitby, Richard J. (2019) First synthesis and characterization of CH4@C60. Angewandte Chemie International Edition, 58 (15), 5038-5043. (doi:10.1002/anie.201900983).

Record type: Article

Abstract

The endohedral fullerene CH4@C60, in which each C60 fullerene cage encapsulates a single methane molecule, has been synthesised for the first time. CH4 is the largest molecule, with the greatest number of atoms, to have been encapsulated in C60 to date. The key orifice contraction step, a photochemical desulfinylation of an open fullerene, was successfully completed, even though it is significantly inhibited by the presence of the endohedral molecule. The 13C NMR resonance for the cage nuclei in CH4@C60 is deshielded by Dd = +0.52 ppm relative to C60. The crystal structure of the nickel(II) octaethylporphyrin / benzene solvate shows no significant distortion of the carbon cage, relative to the C60 analogue, and shows the methane hydrogens as a shell of electron density around the central carbon, indicative of the quantum nature of the methane, existing in a set of quantised rotational-translational states at 100 K. The 1H and 13C spin-lattice relaxation times (T1) for endohedral methane have
been measured. The 1H T1 values are similar to those observed in the gas phase, also indicating that methane is freely rotating inside the C60 cage. The 1H relaxation rate constant T1 -1 increases with increasing temperature and suggests a significant spin-rotation contribution to the relaxation. The successful synthesis of CH4@C60 opens a route to endofullerenes incorporating larger guest molecules than those encapsulated previously.

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More information

Accepted/In Press date: 9 February 2019
e-pub ahead of print date: 18 February 2019
Published date: 1 April 2019
Keywords: endohedral fullerene, Mass spectrometry, NMR Spectroscopy, synthetic methods, X-ray diffraction

Identifiers

Local EPrints ID: 428279
URI: https://eprints.soton.ac.uk/id/eprint/428279
ISSN: 1433-7851
PURE UUID: 42333b7b-6724-4cb7-ba83-73465bd0f77a
ORCID for Sally Bloodworth: ORCID iD orcid.org/0000-0003-2219-3635
ORCID for Mark Light: ORCID iD orcid.org/0000-0002-0585-0843
ORCID for Julie Herniman: ORCID iD orcid.org/0000-0003-4834-1093
ORCID for G. John Langley: ORCID iD orcid.org/0000-0002-8323-7235
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: 20 Feb 2019 17:30
Last modified: 10 Sep 2019 00:57

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Contributors

Author: Gabriela Sitinova
Author: Shamim Alom
Author: Sara Vidal
Author: George, Razvan Bacanu
Author: Stuart J Elliott
Author: Mark Light ORCID iD
Author: Julie Herniman ORCID iD
Author: G. John Langley ORCID iD

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