Improved slow magnetic relaxation in optically pure helicene-based DyIII single molecule magnets.

Racemic and optically pure [Dy(hfac)3(L)] complexes with L = 3-(2-pyridyl)-4-aza[6]-helicene have been synthesized and characterized. Both the racemic and enantiopure forms behave as single molecule magnets in their crystalline phase, while electronic circular dichroism activity is evidenced. Ab initio calculations on isolated complexes followed by the determination of intermolecular dipolar couplings allowed the rationalization of the different low-temperature magnetic behaviours. The enantiopure SMM differs from the racemic one by the presence of a hysteresis loop in the former system.

Rational Design of a Lanthanide-Based Complex Featuring Different Single-Molecule Magnets.

The rational synthesis of the 2-{1-methylpyridine-N-oxide-4,5-[4,5-bis(propylthio)tetrathiafulvalenyl]-1H-benzimidazol-2-yl}pyridine ligand (L) is described. It led to the tetranuclear complex [Dy4(tta)12(L)2] (Dy-Dy2-Dy) after coordination reaction with the precursor Dy(tta)3⋅2 H2O (tta(-) = 2-thenoyltrifluoroacetonate). The X-ray structure of Dy-Dy2-Dy can be described as two terminal mononuclear units bridged by a central antiferromagnetically coupled dinuclear complex. The terminal N2O6 and central O8 environments are described as distorted square antiprisms. The ac magnetism measurements revealed a strong out-of-phase signal of the magnetic susceptibility with two distinct sets of data. The high- and low-frequency components were attributed to the two terminal mononuclear single-molecule magnets (SMMs) and the central dinuclear SMM, respectively. A magnetic hysteresis loop was detected at very low temperature. From both structural and magnetic points of view, the tetranuclear SMM Dy-Dy2-Dy is a self-assembly of two known mononuclear SMMs bridged by a known dinuclear SMM.

Synthesis, crystal structures, and physical properties of the novel Ca(x)R(17-x)Mo19O46 (4 < or = x < or = 7; R = Ce, Pr, Sm, and Gd) compounds containing centered Mo19 nu2-octahedral clusters.

The novel quaternary reduced molybdenum oxides Ca(x)R(17-x)Mo(19)O(46) (4 < or = x < or = 7; R = Ce, Pr, Sm, and Gd) have been synthesized by a solid-state reaction at 1400 degrees C for 48 h in sealed molybdenum crucibles. The crystal structure was determined on a single crystal of Ca(5.24)R(11.76)Mo(19)O(46) by X-ray diffraction. This compound crystallizes in the monoclinic space group C2/m: a = 19.5192(4) A, b = 11.1244(3) A, c = 13.2589(5) A, beta = 132.055(1) degrees, V = 2137.7(1) A(3), Z = 2. Refinements yield R1(F(2)) = 0.0388 and wR2(F(2)) = 0.0792 for 5667 unique reflections. The structure is built up from alternating slabs made up of Mo forming centered Mo(19) nu(2)-octahedral clusters, Ca, Pr, and O atoms and slabs containing only Ca, Pr, and O atoms. The Mo(19) cluster, in which the Mo-Mo distances range from 2.7274(4) to 2.7940(7) A, results from a three-dimensional condensation of six Mo(6) octahedra. The Ca(2+) and Pr(3+) cations occupy seven crystallographically independent sites with coordination numbers in the O atoms varying from 6 to 8. Magnetic susceptibility measurements made on the Ca(x)Pr(17-x)Mo(19)O(46) (x = 4-7) compounds confirm the presence of Pr(3+) cations, and no magnetic ordering was observed down to 4.2 K. Electrical resistivity measurements on a single crystal of Ca(approximately 5)Pr(approximately 12)Mo(19)O(46) show a semiconducting behavior.