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 (HNMR)-H-1 resonance of endohedral NH3 is broadened by scalar coupling to the quadrupolar N-14 nucleus, which relaxes rapidly. This broadening is absent for small satellite peaks, which are attributed to natural abundance N-15. The influence of the scalar relaxation mechanism on the linewidth of the H-1 ammonia resonance is probed by variable temperature NMR. A rotational correlation time of tau(c)=1.5ps. is determined for endohedral NH3, and of tau(c)=57 +/- 5ps. for the open fullerene, indicating free rotation of the encapsulated molecule. IR spectroscopy of NH3@2 at 5K identifies three vibrations of NH3 ((1), (3) and (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 (HNMR)-H-1 spectra indicate that endohedral CH4 is also able to rotate freely at 223K, 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.