Self-Assembly of Extended High-Dimensional Architectures from Anderson-type Polyoxometalate Clusters

Three unusual compounds based on polyoxometalate building blocks, [(C6H5NO2)2Ln(H2O)4]2[IMo6O24][NO3]·4H2O
(Ln = Ce 1 and La 2) and [(H2O)4Ag3][Cr(OH)6Mo6O18]·3H2O 3, have been synthesized and characterized by elemental analysis,
IR and X-ray photoelectron spectroscopy, thermogravimetry analysis, and single-crystal X-ray diffraction. Compounds 1 and 2 are
isostructural and possess a unique two-dimensional (2D) network, which is composed of rare earth coordination polymer chains
joint together by [IMo6O24]5- polyoxoanions, representing the first example of 2D inorganic−organic hybrid compounds based on
A-type Anderson polyoxoanions. Compound 3 is constructed from B-type Anderson polyoxoanions [Cr(OH)6Mo6O18]3- and silver
(I) ions to yield a three-dimensional (3D) open framework containing “guest” water molecules. To our best knowledge, it is the first
time Anderson-type polyoxometalate motifs have been connected with silver ions to construct a 3D covalent framework.