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Read and print from thousands of top scholarly journals. Already have an account? Log in. APA Zhu, Y. Zero-field slow magnetic relaxation from single Co ii ion: a transition metal single-molecule magnet with high anisotropy barrier. Acta Crystallogr. Madison, WI, Physica B Amsterdam, Neth. Rohrer, M. The molecule Results and Discussion crystallizes on an inversion center, so that the asymmetric Syntheses.

The Co II center exhibits a square-pyramidal unit is composed of one-half of the square. The Co II sites geometry, which is typical for most phosphine complexes remain pentacoordinate, with only slight changes to the of Co II , including those with chelating and monodentate metal—ligand coordination sphere as compared to the starting phosphine ligands.

The coordination geometry The compounds are stable both in solution and in the solid phase, except for [CoFe], which is air-sensitive. Also, [CoCo] shows a degree of decomposition during the drying process, which is described in the magnetism section. They are soluble only in DMF and slightly soluble in propylene carbonate.

Single Crystal X-Ray Structures. Figure 1. Figure 2. Space-filling diagrams of the squares depicted from the top and the side. Figure 3. Packing diagrams for compound [CoCo]. A shift compared to those based on octahedrally coordinated metal to higher frequencies is a clear indication of the formation ions.

Also, space-filling diagrams of the cm DC magnetic susceptibility measure- M II are still readily accessible for further substitution ments for the molecular square compounds and the mono- reactions with cyanide precursors, although the bulk of the nuclear building block, Co triphos CN 2, were performed triphos ligand distorts the structure Figure 2. Infrared Spectroscopy. There is which the presence of diamagnetic Zn II results in a simple a positive shift of 23, 24, 36, 37, and 44 cm-1, respectively, paramagnet composed of two mononuclear Co triphos CN 2 Inorganic Chemistry, Vol.

An examination of the ground spin state for [CoMn] was carried out by performing the magnetization measurements at different temperatures in order to determine the zfs parameters more accurately. The where the best fit was obtained by applying the following solid lines correspond to the simulation with the use of the MAGPACK Hamiltonian with the parameters Stotal 4, g 1.

An acceptable model for the magnetization of [CoMn] was achieved using MAG- PACK,45,46 by applying the above Hamiltonian for the low- temperature behavior using the same values for the magnetic parameters obtained from the DC susceptibility measurement.

A spin-Hamiltonian was constructed in the limit of an isotropic exchange interaction, and contains only one J value, Figure 5. Field-dependent magnetization curves for compounds [CoMn] taking advantage of the molecular symmetry eq 2. The zero- 3. The data indicate an absence of magnetic interaction field-splitting parameters of M1 and M2 were set equal to between the two low-spin Co II ions in the molecular square, each other based on the molecular symmetry. The calculated which allows us to make the assumption that the magnetic values are listed in Table 3.

This of magnetometry measurements. Magnetic measure- 7. Table 3. Studies of [CoFe] were further complicated by its being very air-sensitive. For example, g 2. Low- and intermediate-frequency EPR 9. The [CoCo] complex that has been thoroughly dried in the air, however, exhibits a weak, frequency-dependent out-of-phase signal. The dried compound also exhibits a narrow hysteresis loop at 1.

The decomposition product of [CoCo] is unknown but must involve intermolecular interactions. X-band 9. Below 30 K, the presence of low-lying excited states, which arise due to value increases to reach a maximum of 5.

Plots of the at 9 K and then decreases at lower temperatures. The calculated values are listed in Table 3. A g yielded the parameters Stotal 3, g 2. Field-dependent the data are fit assuming antiferromagnetic coupling between magnetization data and simulation using eq 1 are shown in the Co II and Ni II centers. This g value is rather high for Figure 5. The calculated values are listed can be explained by the presence of low-lying excited states, in Table 3. The total cluster spin value, Stotal 3 for [CoFe], leading to the higher effective g value.

That the J and D arises in the same way as that found for [CoMn]. The spins parameters are of the same magnitude could contribute to of the Co II ions are antiferromagnetically coupled to those the difficulty encountered in fitting the data.