ABSTRACT
The spin decoherence of the scandium bimetal in Sc2@C80(CH2Ph) is studied at low temperatures (20-120 K) by the electron spin echo technique. The correlation between the magnetic quantum number m of the total spin state of the scandium nuclei j and the decay rates is established. For the total spin j = 5, a decrease of the phase relaxation time by a factor of two is observed by changing the transition from m = -1 to m = +1 and m = -3 at 120 K. The observed results are rationalized in the framework of the rotational diffusion of the endohedral fragment in the fullerene cage. It is found that the characteristic rotation time is of the order of a microsecond at 100 K and increases at lower temperatures.
ABSTRACT
Measurements of electron paramagnetic resonance (EPR) close to the saturation region of iron-core electromagnets (ca. 1 Tesla) require precise magnetic field calibration due to nonlinear effects. Endohedral fullerenes Sc2@C80(CH2Ph) have unique spectral features due to the large hyperfine interaction (509 MHz) of the delocalized electron with two scandium nuclei (I = 7/2), resulting in a maximum spectral width of 0.25 Tesla. The spectrum consists of 64 well resolved lines divided into 15 groups, depending on the projection of the total spin of the scandium nuclei. Each group has a reference line with the largest possible total nuclear spin, located in the right edge of the group. These reference lines are shown to be equidistant in the low-field and high-field regions of the spectrum, and can therefore serve as a benchmark for magnetic field calibration. The calibration procedure is explained by theoretical calculations and verified on endofullerene spectra in Q-band EPR. To compare the spectral properties, measurements in the X- and W-bands were also performed. Absolute values of magnetic field strength were taken from standard Hall sensors of the spectrometer (X- and Q-bands) or on the measurements of the applied current (W-band); additional control of these values is carried out using a Gaussmeter at the sample location. The results show the high accuracy of the correction procedure for linear and nonlinear magnetic field offsets.
ABSTRACT
Endohedral fullerenes are promising materials for the quantum information and quantum processing due to the unique properties of the electron-nuclear spin system well isolated from the environment inside the fullerene cage. The endofullerene Sc2@C80(CH2Ph) features a strong hyperfine interaction between one electron spin 1/2 localized at the Sc2 dimer and two equivalent 45Sc nuclear spins 7/2, which yields 64 well resolved EPR transitions. We report a comprehensive analysis of the temperature dependence of the EPR spectrum of Sc2@C80(CH2Ph) dissolved in d-toluene measured in a wide temperature range above and below the melting point. The nature of the electron spin coherence phase memory is investigated. The properties of all resonance lines in a liquid phase were treated within the model of the free rotational diffusion. Both, analytical expressions and numerical examination provide an excellent agreement between the experimental and simulated spectra. A detailed study of the experimental data confirms the assumption of the independent motions of the fullerene cage and the Sc2 core. The data obtained show three regimes of molecular motion detected at different temperatures: the free rotation of both the fullerene cage and its bi-metal core, the motion of the core in the frozen fullerene cage, and, finally, a state with a fixed structure of both parts of the metallofullerene molecules. The data analysis reveals a significant nuclear quadrupole interaction playing an important role for the mixing of the different nuclear spin multiplets.
ABSTRACT
We report the synthesis, ESR spectroscopic and spin coherent properties of the dimetallofullerene Sc2@C80(CH2Ph). The single-electron metal-metal bond of the Sc2 dimer inside the fullerene's cage is stabilized with the electron spin density being fully localized at the metal bond. This results in an extraordinary strong hyperfine interaction of the electron spin with the 45Sc nuclear spins with a coupling constant a = 18.2 mT (â¼510 MHz) and yields a fully resolved hyperfine-split ESR spectrum comprising 64 lines. The splitting is present even at low temperatures where the molecular dynamics are completely frozen. The large extent and the robustness of the hyperfine-split spectra enable us to identify and control the well-defined transitions between specific electron-nuclear quantum states. This made it possible to demonstrate in our pulse ESR study the remarkable spin coherent dynamics of Sc2@C80(CH2Ph), such as the generation of arbitrary superpositions of the spin states in a nutation experiment and the spin dephasing times above 10 µs at temperatures T < 80 K reaching the value of 17 µs at T ≤ 20 K. These observations suggest Sc2@C80(CH2Ph) as an interesting qubit candidate and motivate further synthetic efforts to obtain fullerene-based systems with superior spin properties.
ABSTRACT
The unusual temperature behavior of the electron spin resonance (ESR) spectra and magnetic properties are experimentally observed in copper(II) complexes with a dendritic ligand based on the Boltorn H30 polymer (Perstorp Specialty Chemicals AB, Sweden) functionalized with fumaric acid residues in a molar ratio of 1:6. The ESR spectra at low temperatures show signs of transition to higher spin states at temperatures below 8-10 K, and the temperature dependences of the integral ESR signal intensities and magnetic susceptibility show the positive deviation from the Curie-Weiss law, thereby pointing to the presence of ferromagnetic exchange interactions in the system under study. The values of the exchange interaction parameters are calculated by quantum-chemical simulation of the possible structure of the copper(II) complex when assuming the formation of trinuclear coordination sites embedded in the hyperbranched polymer structure. The results of density functional theory calculations indicate the possibility of ferromagnetic exchange through carboxylate bridges in the trinuclear magnetic clusters, and the calculated values of the exchange interaction parameters make it possible to construct theoretical curves of the temperature dependence of the effective magnetic moment, which satisfactorily fit the experimental data, especially considering that polymers are characterized by disperse molecular weights and chemical structures.
ABSTRACT
Spin-polarized echo-detected electron paramagnetic resonance (EPR) spectra and the transversal relaxation rate T2(-1) of the photoexcited triplet state of fullerene C60 molecules were studied in o-terphenyl, 1-methylnaphthalene, and decalin glassy matrices. The model is composed of a fast (correlation time approximately 10(-12) s) pseudorotation of (3)C60 in a local anisotropic potential created by interaction of the fullerene molecule with the surrounding matrix molecules. In simulations, this potential is assumed to be axially symmetric around some axis of a preferable orientation in a matrix cage. The fitted value of the potential was found to depend on the type of glass and to decrease monotonically with a temperature increase. A sharp increase of the T2(-1) temperature dependence was found near 240 K in glassy o-terphenyl and near 100 K in glassy 1-methylnaphthalene and decalin. This increase probably is related to the influence on the pseudorotation of the onset of large-amplitude vibrational molecular motions (dynamical transition in glass) that are known for glasses from neutron scattering and molecular dynamics studies. The obtained results suggest that molecular and spin dynamics of the triplet fullerene are extremely sensitive to molecular motions in glassy materials.
