Synthesis of a Purely Inorganic Three-Dimensional Porous Framework Based on Polyoxometalates and 4d−4f Heterometals

A new polyoxometalate-based 4d−4f heterometallic compound, [{Ag 3 (H 2 O) 2 }{Ce 2 (H 2 O) 12 }H 5 ⊂{H 2 W 11 Ce(H 2 O) 4 O 39 } 2 ]·8H 2 O ( 1 ), has been synthesized and characterized by routine methods. In 1, the dimers constructed by two monosubstituted α-metatungstate [H 2 W 11 {Ce(H 2 O) 4 }O 39 ] 7− (simplified as {W 11 Ce} 7− ) units are linked by Ce III and Ag I to form two-dimensional (2D) networks, and these networks are further connected by Ag I −Ag I ({Ag 2 } 2+ ) bonds to obtain a purely inorganic three-dimensional (3D) framework with two kinds of channels along the [1 0 0] and [0 1 0] directions. Furthermore, 1 exhibits reversible water sorption capability.