A Ferromagnetically Coupled, Bell-Shaped [Ni4Gd5] Cage

Reaction between NiCl2·6H2O, 2-hydroxy-4-methyl-6-phenyl-pyridine-3-amidoxime (H2L), benzoic acid, and M­(NO3)3·6H2O (M = Gd, Y) in MeCN under basic conditions yields the complexes [NiII4GdIII5(PhCOO)10(HL)4(HLzw)4(OH)2(NO3)2]­Cl·13.6MeCN·H2O (1·13.6MeCN·H2O) and [NiII4YIII5(PhCOO)10(HL)4(HLzw)4(OH)2(NO3)1.5(H2O)0.5]­0.5Cl­(NO3)·3H2O (2·3H2O). Both clusters display similar structures, consisting of a bell-shaped {NiII4MIII5} unit, in which a linear “zigzag” {Ni4} subunit bisects the central {MIII5} “ring”. Direct (dc) and alternating current (ac) magnetic susceptibility measurements carried out in the 2–300 K temperature range for complexes 1 and 2 revealed ferromagnetic intermolecular interactions, while heat-capacity measurements for the Gd analogue suggest that complex 1 lowers its temperature from T = 9.6 K down to 2.3 K by adiabatically demagnetizing from Bi = 7 T to Bf = 0.