Pentagonal Bipyramid Fe Complexes: Robust Ising-Spin Units towards Heteropolynuclear Nanomagnets.

Pentagonal bipyramid Fe complexes have been investigated to evaluate their potential as Ising-spin building units for the preparation of heteropolynuclear complexes that are likely to behave as single-molecule magnets (SMMs). The considered monometallic complexes were prepared from the association of a divalent metal ion with pentadentate ligands that have a 2,6-diacetylpyridine bis(hydrazone) core (H L ). Their magnetic anisotropy was established by magnetometry to reveal their zero-field splitting (ZFS) parameter D, which ranged between -4 and -13 cm and was found to be modulated by the apical ligands (ROH versus Cl). The alteration of the D value by N-bound axial CN ligands, upon association with cyanometallates, was also assessed for heptacoordinated Fe as well as for related Ni and Co derivatives. In all cases, N-coordinated cyanide ligands led to large magnetic anisotropy (i.e., -8 to -18 cm for Fe and Ni, +33 cm for Co). Ab initio calculations were performed on three Fe complexes, which enabled one to rationalize the role of the ligand on the nature and magnitude of the magnetic anisotropy. Starting from the pre-existing heptacoordinated complexes, a series of pentanuclear compounds were obtained by reactions with paramagnetic [W(CN) ] . Magnetic studies revealed the occurrence of ferromagnetic interactions between the spin carriers in all the heterometallic systems. Field-induced slow magnetic relaxation was observed for mononuclear Fe complexes (U /k up to 53 K (37 cm ), τ =5×10  s), and SMM behavior was evidenced for a heteronuclear [Fe W ] derivative (U /k =35 K and τ =4.6 10  s), which confirmed that the parent complexes were robust Ising-type building units. High-field EPR spectroscopic investigation of the ZFS parameters for a Ni derivative is also reported.