ABSTRACT
We show that intramolecular exchange disorder recently found in the geometrically frustrated magnetic molecules {Mo(72)Fe(30)} and {Mo(72)Cr(30)} leads, in a classical Heisenberg model description, to spin freezing and slow magnetization dynamics reminiscent of spin glass behaviour. Also we suggest that our low temperature and low magnetic field nuclear magnetic resonance (NMR) measurements on {Mo(72)Fe(30)}, showing rapid and strong broadening of the proton line width on cooling below 600 mK, are evidence for a crossover from paramagnetic behaviour to a frozen spin configuration. Similar broadening is observed in {Mo(72)Cr(30)}. This observed effect is consistent with our theory of spin freezing and slow magnetization dynamics in these systems due to exchange disorder.
ABSTRACT
Inelastic neutron scattering (INS) in variable magnetic field and high-field magnetization measurements in the millikelvin temperature range were performed to gain insight into the low-energy magnetic excitation spectrum and the field-induced level crossings in the molecular spin cluster {Cr(8)}-cubane. These complementary techniques provide consistent estimates of the lowest level-crossing field. The overall features of the experimental data are explained using an isotropic Heisenberg model, based on three distinct exchange interactions linking the eight Cr(III) paramagnetic centers (spins s = 3/2), that is supplemented with a relatively large molecular magnetic anisotropy term for the lowest S = 1 multiplet. It is noted that the existence of the anisotropy is clearly evident from the magnetic field dependence of the excitations in the INS measurements, while the magnetization measurements are not sensitive to its effects.
ABSTRACT
We have developed a nonconventional broadband electron spin resonance (ESR) spectrometer operating continuously in the frequency range from 0.5 to 9 GHz. Dual antenna structure and the microwave absorbing environment differentiate the setup from the conventional one and enable broadband operation with any combination of frequency or magnetic field modulation and frequency or magnetic field sweeping. Its performance has been tested with the measurements on a 1,1-diphenyl-2-picrylhydrazyl (DPPH) sample and with the measurements on the single molecular magnet, V6, in solid state at low temperature.
ABSTRACT
We have observed hysteresis loops and abrupt magnetization steps in the magnetic molecule {V(6)}, where each molecule comprises a pair of identical spin triangles, in the temperature range 1-5 K for external magnetic fields B with sweep rates of several Tesla per millisecond executing a variety of closed cycles. The hysteresis loops are accurately reproduced using a generalization of the Bloch equation based on direct one-phonon transitions between the instantaneous Zeeman-split levels of the ground state (an S=1/2 doublet) of each spin triangle. The magnetization steps occur for B approximately 0, and they are explained in terms of adiabatic Landau-Zener-Stückelberg transitions between the lowest magnetic energy levels as modified by an intertriangle anisotropic exchange of order 0.4 K.
ABSTRACT
Complementary theoretical modeling methods are presented for the classical and quantum Heisenberg model to explain the magnetic properties of nanometer-sized magnetic molecules. Excellent quantitative agreement is achieved between our experimental data down to 0.1 K and for fields up to 60 Tesla and our theoretical results for the giant Keplerate species {Mo72Fe30}, by far the largest paramagnetic molecule synthesized to date.
ABSTRACT
A novel cyclic octanuclear chromium(III) complex with hydroxo and acetato bridging ligands was isolated and its structure determined by X-ray crystallography. The complex [Cr8(OH)12(OAc)12] (1) (OAc- = CH3CO2-), as found in crystals of 1.34H2O, is obtained by refluxing an aqueous solution of the trinuclear "basic" chromium acetate. 1.34H2O crystallizes in the tetragonal space group I42d with the following unit cell dimensions: a = 16.592(2) A, c = 31.557(4) A, V = 8687(1) A3, and Z = 2. A total of 2000 unique data with I > 3 sigma (I) were used to solve and refine the structure to R(Fo) = 0.066 and Rw(Fo) = 0.085. The structure consists of eight Cr(III) ions that form a ring structure and are bridged by hydroxo and acetato ligands. Each of the two neighboring metal atoms in 1 is bridged either by two OH- ligands and one OAc- ligand, with a Cr...Cr distance of 2.949(2) A, or by two OAc- ligands and one OH- ligand, with a Cr...Cr distance of 3.383(2) A in an alternating fashion. The complex resides on a crystallographic 4 center, and the overall symmetry of 1 is S4. The magnetic susceptibility of 1.34H2O was measured in the temperature range of 5-240 K. Our theoretical modeling of the susceptibility data indicates alternating antiferromagnetic exchange interactions between adjacent spin 3/2 Cr3+ ions around the ring, of magnitude J/kB = 13.7 and 8.9 K, respectively.
