Lanthanide Complexes of [α-2-P2W17O61]10-:  Solid State and Solution Studies

• Published in: Inorganic chemistry 2002-11, Vol.41 (23), p.6112-6117
• Main Authors: Luo, Qunhui, Howell, Robertha C, Bartis, Judit, Dankova, Michaela, Horrocks, William DeW, Rheingold, Arnold L, Francesconi, Lynn C
• Format: Article
• Language: English
• Subjects: Chemical Phenomena; Chemistry, Physical; Crystallography, X-Ray; Lanthanoid Series Elements - chemical synthesis; Lanthanoid Series Elements - chemistry; Luminescence; Magnetic Resonance Spectroscopy; Molecular Conformation
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic011187d

We have isolated the 1:1 Ln:[α-2-P2W17O61]10- complexes for a series of lanthanides. The single-crystal X-ray structure of the Eu3+ analogue reveals two identical [Eu(H2O)3(α-2-P2W17O61)]7- moieties connected through two Eu−O−W bonds, one from each polyoxometalate unit. An inversion center relates the two polyoxometalate units. The Eu(III) ion is substituted for a [WO]4+ unit in the “cap” region of the tungsten−oxygen framework of the parent Wells−Dawson ion. The point group of the dimeric molecule is C i . The extended structure is composed of the [Eu(H2O)3(α-2-P2W17O61)]2 14- anions linked together by surface-bound potassium cations. The space group is P1̄, a = 12.7214(5) Å, b = 14.7402(7) Å, c = 22.6724(9) Å, α = 71.550(3)°, β = 84.019(3)°, γ = 74.383(3)°, V = 3883.2(3) Å3, Z = 1. The solution studies, including 183W NMR spectroscopy and luminescence lifetime measurements, show that the molecules dissociate in solution to form monomeric [Ln(H2O)4(α-2-P2W17O61)]7- species.