Trigonal Prismatic Coordination of Discrete Rare Earth Ions, Enforced by the Polyoxotungstate [P4 W27 O99 (H2 O)]16.

A family of solution-stable polyanions [Na⊂{LnIII (H2 O)}{WVI O(H2 O)}PV 4 WVI 26 O98 ]12- (Ln=Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) represent the first examples of polyoxometalates comprising a single lanthanide(III) or yttrium(III) ion in a rare trigonal prismatic O6 environment. Their synthesis exploits the reactivity of the organophosphonate-functionalized precursor [P4 W24 O92 (C6 H5 PV O)2 ]16- with heterometal ions and yields hydrated potassium or mixed lithium/potassium salts of composition Kx Lny H12-x-y [Na⊂{Ln(H2 O)}{WO(H2 O)}P4 W26 O98 ]⋅nH2 O⋅mLiCl (x=8.5-11; y=0-2; n=24-34; m=0-1.5). The Dy, Ho, Er and Yb derivatives are characterized by slow magnetization relaxation.