Dual shell-like magnetic clusters containing NiII and LnIII (Ln = La, Pr, and Nd) ions

Dual shell-like nanoscopic magnetic clusters featuring a polynuclear nickel(II) framework encapsulating that of lanthanide ions (Ln = La, Pr, and Nd) were synthesized using Ni(NO3)(2)center dot 6H(2)O, Ln(NO3)(3) center dot 6H(2)O, and iminodiacetic acid (IDA) under hydrothermal conditions. Structurally established by crystallographic studies, these clusters are [La20Ni30(IDA)(30)(CO3)(6)(NO3)(6)(OH)(30)(H2O)(12)](CO3)(6)center dot 72H(2)O (1), [Ln(20)Ni(21)(C4H5NO4)(2)](OH)(24)(C2H2O3)(6)(C2O4)(3)(NO3)(9)(H2O)(12)](NO3)(9) center dot nH(2)O [C2H2O3 is the alkoxide form of glycolate; Ln = Pr (2), n = 42; Nd (3), n = 50], and {[La4Ni5Na(IDA)(5)(CO3)(NO3)(4)(OH)(5)(H2O)(5)][CO3] center dot 10H(2)O). (4). Carbonate, oxalate, and glycolate are products of hydrothermal decomposition of IDA. Compositions of these compounds were confirmed by satisfactory elemental analyses. It has been found that the cluster structure is dependent on the identity of the lanthanide ion as well as the starting Ln/Ni/IDA ratio, The cationic cluster of 1 features a core of the Keplerate type with an outer icosidodecahedron of Ni-II ions encaging a dodecahedral kernel of La-III. Clusters 2 and 3, distinctly different from 1, are isostructural, possessing a core of an outer shell of 21 Ni-II ions encapsulating an inner shell of 20 Ln(III) ions. Complex 4 is a three-dimensional assembly of cluster building blocks connected by units of Na(NO3)/La(NO3)(3); the structure of the building block resembles closely that of 1, with a hydrated La-III ion internalized in the decanuclear cage being an extra feature. Magnetic studies indicated ferromagnetic interactions in 1, while overall antiferromagnetic interactions were revealed for 2 and 3. The polymeric, three-dimensional cluster network 4 displayed interesting ferrimagnetic interactions.