Persistence of slow dynamics in Tb(OETAP)2 single molecule magnets embedded in conducting polymers.

UNLABELLED: The spin dynamics of Tb(OETAP)2 single ion magnets was investigated by means of muon spin relaxation (µSR) both in the bulk material as well as when the molecule is embedded into PEDOT: PSS polymer conductor. The spin fluctuation time is characterized by a high temperature activated trend, with an energy barrier around 320 K, and by a low temperature tunneling regime. When the single ion magnet is embedded into the polymer the energy barrier only slightly decreases and the fluctuation time remains of the same order of magnitude, even at low temperature. This finding shows that these single molecule magnets preserve their characteristics which, if combined with those of the conducting polymer, result in a hybrid material of potential interest for organic spintronics.

Nuclear magnetic resonance studies of DNP-ready trehalose obtained by solid state mechanochemical amorphization.

(1)H nuclear spin-lattice relaxation and Dynamic Nuclear Polarization (DNP) have been studied in amorphous samples of trehalose sugar doped with TEMPO radicals by means of mechanical milling, in the 1.6-4.2 K temperature range. The radical concentration was varied between 0.34 and 0.81%. The highest polarization of 15% at 1.6 K, observed in the sample with concentration 0.50%, is of the same order of magnitude of that reported in standard frozen solutions with TEMPO. The temperature and concentration dependence of the spin-lattice relaxation rate 1/T1, dominated by the coupling with the electron spins, were found to follow power laws with an exponent close to 3 in all samples. The observed proportionality between 1/T1 and the polarization rate 1/Tpol, with a coefficient related to the electron polarization, is consistent with the presence of Thermal Mixing (TM) and a good contact between the nuclear and the electron spins. At high electron concentration additional relaxation channels causing a decrease in the nuclear polarization must be considered. These results provide further support for a more extensive use of amorphous DNP-ready samples, obtained by means of comilling, in dissolution DNP experiments and possibly for in vivo metabolic imaging.

Dynamic nuclear polarization of a glassy matrix prepared by solid state mechanochemical amorphization of crystalline substances.

A mechanochemical "solvent-free" route is presented for the preparation of solid samples ready to be employed in the Dynamic Nuclear Polarization (DNP). (1)H-DNP build-up curves at 3.46 T as a function of temperature and radical concentration show steady state nuclear polarization of 10% (0.5% TEMPO concentration at 1.75 K).

The role of the glassy dynamics and thermal mixing in the dynamic nuclear polarization and relaxation mechanisms of pyruvic acid.

The temperature dependence of (1)H and (13)C nuclear spin-lattice relaxation rate 1/T1 has been studied in the 1.6-4.2 K temperature range in pure pyruvic acid and in pyruvic acid containing trityl radicals at a concentration of 15 mM. The temperature dependence of 1/T1 is found to follow a quadratic power law for both nuclei in the two samples. Remarkably the same temperature dependence is displayed also by the electron spin-lattice relaxation rate 1/T1e in the sample containing radicals. These results are explained by considering the effect of the structural dynamics on the relaxation rates in pyruvic acid. Dynamic nuclear polarization experiments show that below 4 K the (13)C build up rate scales with 1/T1e, in analogy to (13)C 1/T1 and consistently with a thermal mixing scenario where all the electrons are collectively involved in the dynamic nuclear polarization process and the nuclear spin reservoir is in good thermal contact with the electron spin system.

Strong electronic correlations in LixZnPc organic metals.

Nuclear magnetic resonance, electron paramagnetic resonance and magnetization measurements show that bulk LixZnPc are strongly correlated one-dimensional metals. The temperature dependence of the nuclear spin-lattice relaxation rate 1/T_{1} and of the static uniform susceptibility chi_{S} on approaching room temperature are characteristic of a Fermi liquid. Moreover, while for x approximately 2 the electrons are delocalized down to low temperature, for x-->4 a tendency towards localization is noticed upon cooling, yielding an increase both in 1/T_{1} and chi_{s}. The x dependence of the effective density of states at the Fermi level D(E_{F}) displays a sharp enhancement for x approximately 2, at the half filling of the ZnPc lowest unoccupied molecular orbitals. This suggests that LixZnPc is on the edge of a metal-insulator transition where enhanced superconducting fluctuations could develop.

NMR as a probe of the relaxation of the magnetization in magnetic molecules.

We investigate the time autocorrelation of the molecular magnetization M(t) for three classes of magnetic molecules (antiferromagnetic rings, grids, and nanomagnets), in contact with the phonon heat bath. For all three classes, we find that the exponential decay of the fluctuations of M(t) is characterized by a single characteristic time tau(T,B) for not too high temperature T and field B. This is reflected in a nearly single-Lorentzian shape of the spectral density of the fluctuations. We show that such fluctuations are effectively probed by NMR, and that our theory explains the recent phenomenological observation by Baek et al. [Phys. Rev. B 70, 134434 (2004)] that the Larmor-frequency dependence of 1/T(1) data in a large number of AFM rings fits to a single-Lorentzian form.