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

Xiang Jian Kong, Yan Ping Ren, La Sheng Long, Zhiping Zheng, Gary Nichol, Rong Bin Huang, Lan Sun Zheng

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Abstract

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)2·6H2O, Ln(NO3)3·6H2O, and iminodiacetic acid (IDA) under hydrothermal conditions. Structurally established by crystallographic studies, these clusters are [La20Ni 30(IDA)30(CO3)6(NO3) 6(OH)30(H2O)12](CO3) 6·72H2O (1), [Ln20Ni21 (C4H5NO4)21(OH)24(C 2H2O3)6(C2O 4)3(NO3)9(H2O) 12](NO3)9·nH2O [C 2H2O3 is the alkoxide form of glycolate; Ln = Pr (2), n = 42; Nd (3), n = 50], and {[La4Ni5Na(IDA) 5(CO3)(NO3)4(OH)5(H 2O)5][CO3]·10H2O} (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 NiII ions encaging a dodecahedral kernel of LaIII. Clusters 2 and 3, distinctly different from 1, are isostructural, possessing a core of an outer shell of 21 NiII ions encapsulating an inner shell of 20 LnIII 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 LaIII 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.

Original languageEnglish (US)
Pages (from-to)2728-2739
Number of pages12
JournalInorganic Chemistry
Volume47
Issue number7
DOIs
StatePublished - Apr 7 2008

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Kong, X. J., Ren, Y. P., Long, L. S., Zheng, Z., Nichol, G., Huang, R. B., & Zheng, L. S. (2008). Dual shell-like magnetic clusters containing NiII and Ln III (Ln = La, Pr, and Nd) ions. Inorganic Chemistry, 47(7), 2728-2739. https://doi.org/10.1021/ic702079e