The reaction between Ln(III) chloride and NiCl2·4H2O salts in presence of a multidentate sterically unencumbered ligand, (E)-2,2'-(2-hydroxy-3-((2-hydroxyphenylimino)methyl)-5-methylbenzylazanediyl)diethanol (LH4) leads to the synthesis of four isostructural pentanuclear hetereometallic complexes [Ni2Dy3(LH)4]Cl (1), [Ni2Gd3(LH)4]Cl (2), [Ni2Tb3(LH)3(LH2)]Cl2 (3), [Ni2 Ho3 (LH)3 (LH2)]Cl2 (4) with unprecedented topology. Here the two compounds 1 are 2 are monocationic and crystallize in chiral space group, P2(1)2(1)2(1) whereas compounds 3 and 4 are dicationic and crystallize in achiral space group P2(1)/n. The total metal framework, {Ni2Ln3} unit is held by four triply deprotonated ligands [LH](3-) in 1 and 2 whereas in case of 3 and 4 three triply deprotonated [LH](3-) and one doubly deprotonated [LH2](2-) ligands are involved. In these complexes both the lanthanide ions and the nickel(II) ions are doubly bridged and the bridging is composed of oxygen atoms derived from either phenolate or ethoxide groups. The analysis of SQUID measurements reveal a high magnetic ground state and a slow relaxation of the magnetization with two relaxation regimes for 1. For the thermally activated regime we found an effective energy barrier of U(eff) = 85 K. Micro Hall probe loop measurements directly proof the single-molecule magnet (SMM) nature of 1 with a blocking temperature of T(B) = 3 K and an open hysteresis for sweep rates faster than 50 mT/s.
Keywords: Iron / Spin crossover / Polymorphism / N ligands / Magnetic propertiesThe ligand 2,6-bis(1H-pyrazol-1-yl)-4-(thiocyanatomethyl)-pyridine (L) has been prepared from the hydroxymethyl precursor by OH/Br exchange and subsequent thiocyanate substitution. Two polymorphs of the unsolvated iron(II) complex [Fe(L) 2 ](BF 4 ) 2 crystallize at room temperature from the same solution (MeOH), and side by side. One (yellow) is high spin between 4 and 350 K, whereas the other (red-brown) shows spin crossover, with a thermal spin-transition centred at 272 K (width ca. 50 K). Both forms have been fully charac-
First members of a new family of heterometallic Mn/Ni complexes [Mn(2)Ni(3)X(2)L(4)(LH)(2)(H(2)O)(2)] (X = Cl: 1; X = Br: 2) with the new ligand 2-{3-(2-hydroxyphenyl)-1H-pyrazol-1-yl}ethanol (H(2)L) have been synthesized, and single crystals obtained from CH(2)Cl(2) solutions have been characterized crystallographically. The molecular structures feature a quasi-linear Mn(III)-Ni(II)-Ni(II)-Ni(II)-Mn(III) 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 (J(Mn-Ni) ≈ 40 K (1) or 42 K (2); J(Ni-Ni) ≈ 22 K (1) or 18 K (2)) that lead to an S(tot) = 7 ground state, and a sizable uniaxial magnetoanisotropy with D(mol) 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 U(eff) = 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.
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