The first cobalt molecule to function as a single-molecule magnet, [Co 4 (hmp) 4 (MeOH) 4 Cl 4 ], where hmpis the anion of hydroxymethylpyridine, is reported.The core of the molecule consists of four Co(II) cations and four hmpoxygen atoms ions at the corners of a cube. Variable-field and variable-temperature magnetization data have been analyzed to establish that the molecule has a S=6 ground state with considerable negative magnetoanisotropy. Single-ion zero-field interactions (DS z 2 ) at each cobalt ion are the origin of the negative magnetoanisotropy. A single-crystal of the compound was studied by means of a micro-SQUID magnetometer in the range of 0.040-1.0K.Hysteresis was found in the magnetization versus magnetic field response of this single crystal. It is concluded that this is the first cobalt molecule to function as a singlemolecule magnet.

A series of Ni(4) cubane complexes with the composition [Ni(hmp)(ROH)Cl](4) complexes 1-4 where R= -CH(3) (complex 1), -CH(2)CH(3) (complex 2), -CH(2)CH(2)(C(4)H(9)) (complex 3), -CH(2)CH(2)CH(2)(C(6)H(11)) (complex 4), hmp(-) is the anion of 2-hydroxymethylpyridine, t-Buhmp(-) is the anion of 4-tert-butyl-2-hydroxymethylpyridine, and dmb is 3,3-dimethyl-1-butanol] and [Ni(hmp)(dmb)Br](4) (complex 5) and [Ni(t-Buhmp)(dmb)Cl](4) (complex 6) were prepared. All six complexes were characterized by dc magnetic susceptibility data to be ferromagnetically coupled to give an S = 4 ground state with significant magnetoanisotropy (D approximately equal to -0.6 cm(-1)). Magnetization hysteresis measurements carried out on single crystals of complexes 1-6 establish the single-molecule magnet (SMM) behavior of these complexes. The exchange bias observed in the magnetization hysteresis loops of complexes 1 and 2 is dramatically decreased to zero in complex 3, where the bulky dmb ligand is employed. Fast tunneling of magnetization is observed for the high-symmetry (S(4) site symmetry) Ni(4) complexes in the crystal of complex 3, and the tunneling rate can even be enhanced by destroying the S(4) site symmetry, as is the case for complex 4, where there are two crystallographically different Ni(4) molecules, one with C(2) and the other with C(1) site symmetry. Magnetic ordering temperatures due to intermolecular dipolar and magnetic exchange interactions were determined by means of very low-temperature ac susceptibility measurements; complex 1 orders at 1100 mK, complex 3 at 290 mK, complex 4 at approximately 80 mK, and complex 6 at <50 mK. This confirms that bulkier ligands correspond to more isolated molecules, and therefore, magnetic ordering occurs at lower temperatures for those complexes with the bulkiest ligands.

No abstract

Electron paramagnetic resonance ͑EPR͒ studies of a Ni 4 single-molecule magnet ͑SMM͒ yield the zerofield-splitting ͑ZFS͒ parameters D, B 4 0 , and B 4 4 , based on the giant spin approximation ͑GSA͒ with S =4; B 4 4 is responsible for the magnetization tunneling in this SMM. Experiments on an isostructural Ni-doped Zn 4 crystal establish the Ni II ion ZFS parameters. The fourth-order ZFS parameters in the GSA arise from the interplay between the Heisenberg interaction Jŝ 1 • ŝ 2 and the second-order single-ion anisotropy, giving rise to mixing of higher-lying S 4 states into the S = 4 state. Consequently, J directly influences the ZFS in the ground state, enabling its determination by EPR.