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

A new polyoxometalate-based 4d−4f heterometallic compound, [{Ag3(H2O)2}{Ce2(H2O)12}H5⊂{H2W11Ce(H2O)4O39}2]·8H2O (1), has been synthesized and characterized by routine methods. In 1, the dimers constructed by two monosubstituted α-metatungstate [H2W11{Ce(H2O)4}O39]7− (simplified as {W11Ce}7−) units are linked by CeIII and AgI to form two-dimensional (2D) networks, and these networks are further connected by AgI−AgI ({Ag2}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.