Coordination of Rare-Earth Elements in Complexes with Monovacant Wells−Dawson Polyoxoanions

• Published in: Inorganic chemistry 2001-04, Vol.40 (8), p.1894-1901
• Main Authors: Luo, Qun-Hui, Howell, Robertha C, Dankova, Michaela, Bartis, Judit, Williams, Clayton W, Horrocks, William DeW, Young, Victor G, Rheingold, Arnold L, Francesconi, Lynn C, Antonio, Mark R
• Format: Article
• Language: English
• Subjects: Anions - chemistry; Luminescence; Metals, Rare Earth - chemistry; Molecular Structure; Spectrophotometry; Tungsten Compounds - chemistry; X-Ray Diffraction
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic001427+

The α-1 and α-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]17- (for Ln ≡ Sm, Eu, Lu; X ≡ P, As). The crystal and molecular structures of [(H2O)4Lu(α-1-P2W17O61)]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-P2W17O61)]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-P2W17O61)]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.