Coordination of rare-earth elements in complexes with monovacant Wells-Dawson polyoxoanions

Q. H. Luo, R. C. Howell, M. Dankova, J. Bartis, C. W. Williams, Jr D.W. Horrocks, Jr G. Young, A. L. Rheingold, L. C. Francesconi, M. R. Antonio

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The α-1 and β-2 isomers of the monovacant Wells-Dawson heteropolyoxoanion [P2W17O61]10- are complexants of trivalent rare-earth (RE) ions and serve to stabilize otherwise reactive tetravalent lanthanide (Ln) and actinide (An) ions in aqueous solution. Aspects of the bonding of Ln ions with α-1-[P2W17O61]10- and α-2-[P2W17O61]10- were investigated to address issues of complex formation and stability. We present structural insights about the Ln(III) coordination environment and hydration in two types of stoichiometric complexes, [Ln(α-1-P2W17O61)]7- and [Ln(α-2-X2W17O61)2] 7- (for Ln ≡ Sm, Eu, Lu; X ≡ P, As). The crystal and molecular structures of [(H2O)4-Lu(α-1-P 2W17O61)]7- (1) and [Lu(α-2-P2W17O61)2] 17- (2) were solved and refined through use of single-crystal X-ray diffraction. The crystallographic results are supported with corresponding insights from XAFS (X-ray absorption fine structure) for a series of nine solid-state complexes as well as from optical luminescence spectroscopy of the Eu(III) analogues in aqueous solution. All the Ln ions are eight-coordinate with oxygen atoms in a square antiprism arrangement. For the 1:1 stoichiometric Ln/α-1-[P2W17O61]10- complexes, the Ln ions are bound to four O atoms of the lacunary polyoxometalate framework in addition to four O atoms from solvent (water) molecules as [(H2O)4Ln(α-1-P2 W17O61)]7-. This structure (1) is the first of its kind for any metal complex of α-1-[P2W17O61]10-, and the data indicate that the general stoichiometry [(H2O)4Ln(α-1-P2W 17O61)]7- is maintained throughout the lanthanide series. For the 1:2 stoichiometric Ln/α-2-[X2W17O61]10- complexes, no water molecules are in the Ln-O8 coordination sphere. The Ln ions are bound to eight O atoms-four from each of two heteropolyanions-as [Ln(α-2-X2W17O61)2] 17-. The average Ln-O interatomic distances decrease across the lanthanide series, consistent with the decreasing Ln ionic radius.

Original languageEnglish (US)
Pages (from-to)1894-1901
Number of pages8
JournalInorganic chemistry
Issue number8
StatePublished - Apr 9 2001


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