Large cluster formation through multiple substitution with lanthanide cations (La, Ce, Nd, Sm, Eu, and Gd) of the polyoxoanion.

Several new large polyoxotungstates have been synthesized by reaction of lanthanide cations with the well-known "As(4)W(40)" anion, (B-alpha-AsO(3)W(9)O(30))(4)(WO(2))(4) (1). The heteropolyanions (H(2)O)(11)Ln(III)(Ln(III)(2)OH)(B-alpha-AsO(3)W(9)O(30))(4)(WO(2))(4)(-) (Ln = Ce, Nd, Sm, Gd) (2-4) (Ln(3)As(4)W(40)) and M(m)()(H(2)O)(10)(Ln(III)(2)OH)(2)(B-alpha-AsO(3)W(9)O(30))(4)(WO(2))(4) (Ln = La, Ce, Gd and M = Ba, K, none) (5-7) (Ln(4)As(4)W(40)) have been isolated as alkali metal and ammonium salts, respectively, and characterized by single-crystal X-ray analysis, elemental analysis, and IR and (183)W-NMR spectroscopy. The X-ray analyses revealed interanionic W-O-Ln bonds between adjacent Ln(x)()As(4)W(40) units forming a "dimer" for x = 3 and chains for x = 4. Upon dissolving in water these bonds hydrolyze and the monomeric species form. The straightforward syntheses which require the use of concentrated NaCl solutions (1-4 M) and the addition of stoichiometric amounts of Ba(2+) or K(+) reemphasize the importance of the presence of appropriate countercations for the assembly of large polyoxometalate structures.