Tellurite-Squarate Driven Assembly of a New Family of Nanoscale Clusters Based on (Mo2 O2 S2 )2.

The preparation and characterization of a new family of four polyoxothiometalate (POTM) clusters are reported, with varying size and complexity, based upon the dimeric [Mo2 O2 S2 (H2 O)6 ]2+ cation with the general formula (NMe4 )a Kb [(Mo2 O2 S2 )c (TeO4 )d (C4 O4 )e (OH)f ] where a,b,c,d,e,f={1,7,14,2,4,10}=1, {Mo28 Te2 }; {2,26,36,12,10,48}=2, {Mo72 Te12 }; {0,11,15,3,3,21}=3, {Mo30 Te3 }; {2,6,12,2,4,16}=4, {Mo24 Te2 }. The incorporation of tellurite anions allowed the fine tuning of the templating and bridging of the available building blocks, leading to new topologies of increased complexity. The structural diversity of this family of compounds ranges from the highly symmetrical cross-shaped {Mo24 Te2 } to the stacked ring structure of {Mo72 Te12 }, which is the largest tellurium-containing POTM cluster reported so far. Also a detailed experimental analysis revealed that the pH isolation window extends from acidic to basic values. ESI-MS analyses not only confirmed the stability of this family in solution but also revealed the stability of the observed virtual building blocks.