Benno Meier

The dipolar endofullerene HF@C60

The cavity inside fullerenes provides a unique environment for the study of isolated atoms and molecules. We report the encapsulation of hydrogen fluoride inside C60 using molecular surgery to give the endohedral fullerene HF@C60. The key synthetic step is the closure of the open fullerene cage with the escape of HF minimized. 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 J coupling typical of an isolated species. The dipole moment of HF@C60 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.

Long-Lived Nuclear Spin States in Methyl Groups and Quantum-Rotor-Induced Polarization

Substances containing rapidly rotating methyl groups may exhibit long-lived states (LLSs) in solution, with relaxation times substantially longer than the conventional spin-lattice relaxation time T1. The states become long-lived through rapid internal rotation of the CH3 group, which imposes an approximate symmetry on the fluctuating nuclear spin interactions. In the case of very low CH3 rotational barriers, a hyperpolarized LLS is populated by thermal equilibration at liquid helium temperature. Following dissolution, cross-relaxation of the hyperpolarized LLS, induced by heteronuclear dipolar couplings, generates strongly enhanced antiphase NMR signals. This mechanism explains the NMR signal enhancements observed for (13)C-γ-picoline (Icker, M.; Berger, S. J. Magn. Reson. 2012, 219, 1-3).

Nuclear spin conversion of water inside fullerene cages detected by low-temperature nuclear magnetic resonance

The water-endofullerene H2O@C60 provides a unique chemical system in which freely rotating water molecules are confined inside homogeneous and symmetrical carbon cages. The spin conversion between the ortho and para species of the endohedral H2O was studied in the solid phase by low-temperature nuclear magnetic resonance. The experimental data are consistent with a second-order kinetics, indicating a bimolecular spin conversion process. Numerical simulations suggest the simultaneous presence of a spin diffusion process allowing neighbouring ortho and para molecules to exchange their angular momenta. Cross-polarization experiments found no evidence that the spin conversion of the endohedral H2O molecules is catalysed by (13)C nuclei present in the cages.

Theory of long-lived nuclear spin states in methyl groups and quantum-rotor induced polarisation

Long-lived nuclear spin states have a relaxation time much longer than the longitudinal relaxation time T1. Long-lived states extend significantly the time scales that may be probed with magnetic resonance, with possible applications to transport and binding studies, and to hyperpolarised imaging. Rapidly rotating methyl groups in solution may support a long-lived state, consisting of a population imbalance between states of different spin exchange symmetries. Here, we expand the formalism for describing the behaviour of long-lived nuclear spin states in methyl groups, with special attention to the hyperpolarisation effects observed in (13)CH3 groups upon rapidly converting a material with low-barrier methyl rotation from the cryogenic solid state to a room-temperature solution [M. Icker and S. Berger, J. Magn. Reson. 219, 1 (2012)]. We analyse the relaxation properties of methyl long-lived states using semi-classical relaxation theory. Numerical simulations are supplemented with a spherical-tensor analysis, which captures the essential properties of methyl long-lived states.

Electrical detection of ortho-para conversion in fullerene-encapsulated water

Water exists in two spin isomers, ortho and para, that have different nuclear spin states. In bulk water, rapid proton exchange and hindered molecular rotation obscure the direct observation of two spin isomers. The supramolecular endofullerene H2O@C60 provides freely rotating, isolated water molecules even at cryogenic temperatures. Here we show that the bulk dielectric constant of this substance depends on the ortho/para ratio, and changes slowly in time after a sudden temperature jump, due to nuclear spin conversion. The attribution of the effect to ortho–para conversion is validated by comparison with nuclear magnetic resonance and quantum theory. The change in dielectric constant is consistent with an electric dipole moment of 0.51±0.05 Debye for an encapsulated water molecule, indicating the partial shielding of the water dipole by the encapsulating cage. The dependence of bulk dielectric constant on nuclear spin isomer composition appears to be a previously unreported physical phenomenon.

Enhancement of quantum rotor NMR signals by frequency-selective pulses.

Quantum-rotor-induced polarisation (QRIP) enhancement is exhibited by substances which contain freely rotating methyl groups in the solid state, provided that the methyl groups contain a (13)C nucleus. Strong signal enhancements are observed in solution NMR when the material is first equilibrated at cryogenic temperatures, then rapidly dissolved with a warm solvent and transferred into an NMR magnet. QRIP leads to strongly-enhanced (13)C NMR signals, but relatively weak enhancements of the (1)H signals. We show that the (1)H signals suffer from a partial cancellation of degenerate contributions, which may be corrected by applying a frequency-selective π pulse to the inner peaks of the (13)C multiplet prior to (1)H observation.

Dynamic nuclear polarization of long-lived nuclear spin states in methyl groups

We have induced hyperpolarized long-lived states in compounds containing 13C-bearing methyl groups by dynamic nuclear polarization (DNP) at cryogenic temperatures, followed by dissolution with a warm solvent. The hyperpolarized methyl long-lived states give rise to enhanced antiphase 13C NMR signals in solution, which often persist for times much longer than the 13C and 1H spin-lattice relaxation times under the same conditions. The DNP-induced effects are similar to quantum-rotor-induced polarization (QRIP) but are observed in a wider range of compounds because they do not depend critically on the height of the rotational barrier. We interpret our observations with a model in which nuclear Zeeman and methyl tunnelling reservoirs adopt an approximately uniform temperature, under DNP conditions. The generation of hyperpolarized NMR signals that persist for relatively long times in a range of methyl-bearing substances may be important for applications such as investigations of metabolism, enzymatic reactions, protein-ligand binding, drug screening, and molecular imaging.

Nuclear magnetic resonance apparatus for pulsed high magnetic fields

A nuclear magnetic resonance apparatus for experiments in pulsed high magnetic fields is described. The magnetic field pulses created together with various magnet coils determine the requirements such an apparatus has to fulfill to be operated successfully in pulsed fields. Independent of the chosen coil it is desirable to operate the entire experiment at the highest possible bandwidth such that a correspondingly large temporal fraction of the magnetic field pulse can be used to probe a given sample. Our apparatus offers a bandwidth of up to 20 MHz and has been tested successfully at the Hochfeld-Magnetlabor Dresden, even in a very fast dual coil magnet that has produced a peak field of 94.2 T. Using a medium-sized single coil with a significantly slower dependence, it is possible to perform advanced multi-pulse nuclear magnetic resonance experiments. As an example we discuss a Carr-Purcell spin echo sequence at a field of 62 T.

Eigenmodes in the long-time behavior of a coupled spin system measured with nuclear magnetic resonance.

The many-body quantum dynamics of dipolar coupled nuclear spins I=1/2 on an otherwise isolated cubic lattice are studied with nuclear magnetic resonance. By increasing the signal-to-noise ratio by 2 orders of magnitude compared with previous reports for the free induction decay (FID) of (19)F in CaF(2) we obtain new insight into its long-time behavior. We confirm that the tail of the FID is an exponentially decaying cosine, but our measurements reveal a second decay mode with comparable frequency but twice the decay constant. This result is in agreement with a recent theoretical prediction for the FID in terms of eigenvalues for the time evolution of chaotic many-body quantum systems.

NMR lineshapes and scalar relaxation of the 17O-labelled water-endofullerene H2O@C60

The 17 O isotopomer of the water-endofullerene H2 O@C60 displays a remarkable proton NMR spectrum, with six well resolved peaks. These peaks are due to the J-coupling between the water protons and the 17 O nucleus, which has spin-5/2. The resolution of these peaks is enabled by the suppression of water proton exchange by the fullerene cage. The six peaks display an unusual pattern of linewidths, which we model by a Liouville-space treatment of scalar relaxation due to quadrupolar relaxation of the 17 O nuclei. The data are consistent with rotational diffusion of the water molecules on the sub-picosecond timescale.