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

Pentagonal bipyramid Fe^II 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 (H₂ L^N3O2R ). Their magnetic anisotropy was established by magnetometry to reveal their zero-field splitting (ZFS) parameter D, which ranged between -4 and -13 cm^-1 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^II as well as for related Ni^II and Co^II derivatives. In all cases, N-coordinated cyanide ligands led to large magnetic anisotropy (i.e., -8 to -18 cm^-1 for Fe and Ni, +33 cm^-1 for Co). Ab initio calculations were performed on three Fe^II 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)₈ ]^3- . 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^II complexes (U_eff /k_B up to 53 K (37 cm^-1 ), τ₀ =5×10^-9  s), and SMM behavior was evidenced for a heteronuclear [Fe₃ W₂ ] derivative (U_eff /k_B =35 K and τ₀ =4.6 10^-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.