Tellurite‐Squarate Driven Assembly of a New Family of Nanoscale Clusters Based on (Mo(2)O(2)S(2))(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 [Mo(2)O(2)S(2)(H(2)O)(6)](2+) cation with the general formula (NMe(4))(a)K(b)[(Mo(2)O(2)S(2))(c)(TeO(4))(d)(C(4)O(4))(e)(OH)(f)] where a,b,c,d,e,f={1,7,14,2,4,10}=1, {Mo(28)Te(2)}; {2,26,36,12,10,48}=2, {Mo(72)Te(12)}; {0,11,15,3,3,21}=3, {Mo(30)Te(3)}; {2,6,12,2,4,16}=4, {Mo(24)Te(2)}. 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 {Mo(24)Te(2)} to the stacked ring structure of {Mo(72)Te(12)}, 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.