Assembly of inorganic [MoSO] panels connected by selenite anions to nanoscale chalcogenide-polyoxometalate clusters.

We describe how supramolecular assembly, mediated by control of the ratio of the hetero-atoms in the units [MoSO] and SeO leads to the formation of new types of building blocks, [(MoOS)(OH)(HO)(SeO)] = {Mo} and [(MoOS)(OH)(HO)(SeO)] = {Mo} which are linked in an type of inorganic 'panelling' to the assembly of a range of new clusters with the general formula {(MoOS) (OH) (SeO) (HO) } , where , , , , = [8, 0, 20, 8, 24] for , [14, 14, 17, 8, 20] for and [8, 8, 8, 0, 8] for . Cluster , a rare example of inorganic cryptand, exhibits an elliptical "endo" motif defining an anisotropic ellipse with the dimensions 1.7 × 1.0 nm, with pores ranging from 5.3 to 6.4 Å and site selective cation recognition properties; cluster exhibits an "exo" structural motif constructed by 3 × {Mo} and 2 × {Mo} panels spanning a cross shape 2.4 × 2.0 nm and cluster a ring shaped structure of a 1.5 nm in diameter. The control of endo exo topology as a function of the Se : Mo ratio is reflected to the difference in surface area of 500 Å between clusters and intermolecular interactions and proton conduction properties, and this work shows that very simple synthetic parameters can critically change the structure and properties of all-inorganic nanoscale chalcogenide-polyoxometalates.