Synthesis and Properties of Open Fullerenes Encapsulating Ammonia and Methane. Issue 3 (4th January 2018)

• Record Type: Journal Article
• Authors: Bloodworth, Sally; Gräsvik, John; Alom, Shamim; Kouřil, Karel; Elliott, Stuart J.; Wells, Neil J.; Horsewill, Anthony J.; Mamone, Salvatore; Jiménez‐Ruiz, Mónica; Rols, Stéphane; Nagel, Urmas; Rõõm, Toomas; Levitt, Malcolm H.; Whitby, Richard J.
• Is Part Of: Chemphyschem. Volume 19:Issue 3(2018)
• Page Start: 266
• Page End: 276
• Publication Date: 2018-01-04
• Subjects: endofullerenes -- inelastic neutron scattering spectroscopy -- infra-red spectroscopy -- NMR spectroscopy -- SpinDynamica; Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1002/cphc.201701212
• Languages: English
• ISSNs: 1439-4235

Abstract

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 1 H NMR resonance of endohedral NH3 is broadened by scalar coupling to the quadrupolar 14 N nucleus, which relaxes rapidly. This broadening is absent for small satellite peaks, which are attributed to natural abundance 15 N. The influence of the scalar relaxation mechanism on the linewidth of the 1 H 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 ( ν 1, ν 3 and ν 4 ) 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 1 H 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 . Abstract : Trapped ! Encapsulation of a single molecule of ammonia or methane in open‐cage C60 derivatives is achieved. Free rotation of NH3 and CH4 within each fullerene cage is determined by NMR spectroscopy and the complexes are further characterised by inelastic neutron scattering spectroscopy and infra‐red spectroscopy.