Abstract:The cavity inside fullerenes provides a unique environment for the study of isolated atoms and molecules. We report encapsulation of hydrogen fluoride inside C 60 using molecular surgery to give the endohedral fullerene HF@C 60 . The key synthetic step is the closure of the open fullerene cage while minimizing escape of HF. The encapsulated HF molecule moves freely inside the cage and exhibits quantization of its translational and rotational degrees of freedom, as revealed by inelastic neutron scattering and infrared spectroscopy. The rotational and vibrational constants of the encapsulated HF molecules were found to be redshifted relative to free HF. The NMR spectra display a large 1 H-19 F Jcoupling typical of an isolated species. The dipole moment of HF@C 60 was estimated from the temperature-dependence of the dielectric constant at cryogenic temperatures and showed that the cage shields around 75% of the HF dipole.Molecular endofullerenes consist of fullerene cages encapsulating small molecules, which are free to rotate and translate inside the cage. 1 The dihydrogen and water endofullerenes H 2 @C 60 , H 2 O@C 60 , and their isotopologues, have been synthesized by the procedure known as 'molecular surgery', in which synthetic operations are used to open a hole in the fullerene allowing encapsulation of the guest, followed by a suturing technique to reform the pristine fullerene shell. [2][3][4] Recently the approach has been extended to C 70 and C 59 N. [5][6][7] The confined molecules display quantization of their coupled translational and rotational degrees of freedom, and exhibit phenomena such as nuclear spin isomerism and orthopara conversion. [8][9][10][11][12] Recently it was shown that nuclear spin conversion of the encapsulated water molecules in H 2 O@C 60 leads to a change in the dielectric constant of the material. 13 One system of great interest is HF@C 60 , in which each fullerene cage contains a single hydrogen fluoride (HF) molecule. This material offers the possibility to study the spectroscopic properties of nearisolated and freely rotating HF molecules under a wide range of conditions, free from the complications of dimerization and hydrogen bonding. Predictions of the properties of HF@C 60 have been made using classical, 14 semiempirical 15,16 and quantum chemistry techniques. [17][18][19][20] Furthermore it has been postulated that endofullerenes containing freely rotating electric dipoles could exhibit ferroelectricity, due to cooperative alignment of the interacting electric dipole moments. 21 2The first examples of open-cage endofullerenes encapsulating a hydrogen fluoride molecule have recently appeared, including HF@1. 22,23 Herein we report the successful suturing of HF@1 to give the closed-cage species HF@C 60 . We present NMR, infrared, and neutron scattering data on HF@C 60 which show that the translational and rotational motions of the HF molecule inside the cage are quantized. Interactions with the cage modify the rotational and vibrational constants of the encapsula...

Inelastic neutron scattering, far-infrared spectroscopy, and cryogenic nuclear magnetic resonance are used to investigate the quantized rotation and ortho-para conversion of single water molecules trapped inside closed fullerene cages. The existence of metastable ortho-water molecules is demonstrated, and the interconversion of ortho-and para-water spin isomers is tracked in real time. Our investigation reveals that the ground state of encapsulated ortho water has a lifted degeneracy, associated with symmetry-breaking of the water environment.

No abstract

a Inelastic neutron scattering (INS) has been employed to investigate the quantum dynamics of water molecules permanently entrapped inside the cages of C 60 fullerene molecules. This study of the supramolecular complex, H 2 O@C 60 , provides the unique opportunity to study isolated water molecules in a highly symmetric environment. Free from strong interactions, the water molecule has a high degree of rotational freedom enabling its nuclear spin isomers, ortho-H 2 O and para-H 2 O to be separately identified and studied. The INS technique mediates transitions between the ortho and para spin isomers and using three INS spectrometers, the rotational levels of H 2 O have been investigated, correlating well with the known levels in gaseous water. The slow process of nuclear spin conversion between ortho-H 2 O and para-H 2 O is revealed in the time dependence of the INS peak intensities over periods of many hours. Of particular interest to this study is the observed splitting of the ground state of ortho-H 2 O, raising the three-fold degeneracy into two states with degeneracy 2 and 1 respectively. This is attributed to a symmetry-breaking interaction of the water environment.

No abstract

We present an overview of solid-state NMR studies of endohedral H(2)-fullerene complexes, including (1)H and (13)C NMR spectra, (1)H and (13)C spin relaxation studies, and the results of (1)H dipole-dipole recoupling experiments. The available data involves three different endohedral H(2)-fullerene complexes, studied over a wide range of temperatures and applied magnetic fields. The symmetry of the cage influences strongly the motionally-averaged nuclear spin interactions of the endohedral H(2) species, as well as its spin relaxation behaviour. In addition, the non-bonding interactions between fullerene cages are influenced by the presence of endohedral hydrogen molecules. The review also presents several pieces of experimental data which are not yet understood, one example being the structured (1)H NMR lineshapes of endohedral H(2) molecules trapped in highly symmetric cages at cryogenic temperatures. This review demonstrates the richness of NMR phenomena displayed by H(2)-fullerene complexes, especially in the cryogenic regime.

No abstract

We have observed 1H NMR spectra of hydrogen molecules trapped inside modified fullerene cages under cryogenic conditions. Experiments on static samples were performed at sample temperatures down to 4.3 K, while magic-angle-spinning (MAS) experiments were performed at temperatures down to 20 K at spinning frequencies of 15 kHz. Both types of NMR spectra show a large increase in the intramolecular 1H-1H dipolar coupling at temperatures below 50 K, revealing thermal selection of a small number of spatial rotational states. The static and MAS spectra were compared to estimate the degree of sample heating in high-speed cryogenic MAS-NMR experiments. The cryogenic MAS-NMR data show that the site resolution of magic-angle-spinning NMR may be combined with the high signal strength of cryogenic operation and that cryogenic phenomena may be studied with chemical site selectivity.