Magnetostructural correlations in the tetranuclear series of {Fe3LnO2} butterfly core clusters: Magnetic and Moumlssbauer spectroscopic study

Six tetranuclear complexes [Fe(III)(3)Ln(mu(3)-O)(2)(CCl3COO)(8)(H2O)(THF)(3)]center dot THF center dot C7H16 [Ln=Gd(III) (1), Tb(III) (2), Dy(III) (3), Ho(III) (4), Y(III) (5), and Lu(III) (6)] have been studied by magnetic susceptibility and Moumlssbauer spectroscopy. These isostructural molecules have a "butterfly" structure core consisting of two Fe(2)Ln(mu(3)-O) triangular "wings" which share a common Ln-Fe "body"; the dihedral angle between the wings is ca. 148 degrees. The coordination spheres of the iron ions are essentially distorted octahedral. The lanthanides are eight-coordinate with coordination polyhedra that may be described as distorted tetragonal bipyramids. Variable-temperature solid-state magnetic susceptibility in the temperature range 1.8-300 K and magnetization at 1.8 K for compounds 1-6 were measured. The spin state of Fe is S=5/2 in all cases. In compounds 5 and 6, where Ln(III) (Y and Lu, respectively) is diamagnetic, the three Fe atoms form an obtuse isosceles triangle with antiferromagnetic interactions J(Fe-Fe)=-50 K between the wing-tip Fe-w and body Fe-b atoms, and negligible interaction between the Fe-w's, resulting in a ground state of effective spin S=5/2 per cluster. In the complexes with paramagnetic lanthanide ions, the interaction between the Fe-3 triangle and the Ln(III) center is described by an effective exchange constant which is antiferromagnetic and 1 order of magnitude weaker. Besides, at 3 K incipient spin blocking, characteristic of single molecule magnets, was found to occur in the out-of-phase component of the ac susceptibility in {Fe3TbO2}, {Fe3DyO2}, and {Fe3HoO2}. The activation energy of a Debye process describing the magnetization reversal has been determined to be, E-a approximate to 8, 9, and 10 K for the Ln=Tb, Dy, and Ho, respectively, and the prefactor tau(0)approximate to 10(-7) s. The high spin states of the Fe(III) centers were confirmed by the Moumlssbauer spectra, in which two distinguishable Fe sites could be resolved above 80 K, corresponding to the Fe-w and Fe-b sites, respectively. Relatively larger values of the quadrupole splitting of the Moumlssbauer spectra were observed for the Fe-w pair as compared with that for the Fe-b, and both quadrupole splittings diminished with increasing temperature. At 3 K the Moumlssbauer spectra showed a state with blocked spins (sextets) for the {Fe3TbO2} and {Fe3DyO2} cases. From the E-a and tau(0), determined in the ac susceptibility, the relaxation time at 3 K is estimated as tau approximate to 10(-5)-10(-6) s much longer than the time window of Moumlssbauer spectroscopy and compatible with the single molecule magnet behavior. In the presence of a strong magnetic field the moments of the Ln(III) cation and the Fe-3 triangle are polarized. For some compounds at low temperature a magnetic pattern (sextet) for each of the three Fe sites appeared, and the antiferromagnetic coupling within the Fe-3 cluster was directly proved by the opposite trend of the field dependence of the two Fe-w sextets as compared with the Fe-b third one.