A New Family of 1D Exchange Biased Heterometal Single-Molecule Magnets: Observation of Pronounced Quantum Tunneling Steps in the Hysteresis Loops of Quasi-Linear {Mn2Ni3} Clusters

First members of a new family of heterometallic Mn/Ni complexes [Mn2Ni3X2L4(LH)2(H2O)2] (X = Cl: 1; X = Br: 2) with the new ligand 2-{3-(2-hydroxyphenyl)-1H-pyrazol-1-yl}ethanol (H2L) have been synthesized, and single crystals obtained from CH2Cl2 solutions have been characterized crystallographically. The molecular structures feature a quasi-linear MnIII−NiII−NiII−NiII−MnIII core with six-coordinate metal ions, where elongated axes of all the distorted octahedral coordination polyhedra are aligned parallel and are fixed with respect to each other by intramolecular hydrogen bonds. 1 and 2 exhibit quite strong ferromagnetic exchange interactions throughout (JMn−Ni ≈ 40 K (1) or 42 K (2); JNi−Ni ≈ 22 K (1) or 18 K (2)) that lead to an Stot = 7 ground state, and a sizable uniaxial magnetoanisotropy with Dmol values −0.55 K (1) and −0.45 K (2). These values are directly derived also from frequency- and temperature-dependent high-field EPR spectra. Slow relaxation of the magnetization at low temperatures and single-molecule magnet (SMM) behavior are evident from frequency-dependent peaks in the out-of-phase ac susceptibilities and magnetization versus dc field measurements, with significant energy barriers to spin reversal Ueff = 27 K (1) and 22 K (2). Pronounced quantum tunnelling steps are observed in the hysteresis loops of the temperature- and scan rate-dependent magnetization data, but with the first relaxation step shifted above (1) or below (2) the zero crossing of the magnetic field, despite the very similar molecular structures. The different behavior of 1 and 2 is interpreted in terms of antiferromagnetic (1) or ferromagnetic (2) intermolecular interactions, which are discussed in view of the subtle differences of intermolecular contacts within the crystal lattice.