Spontaneous formation of a chiral (Mo2O2S2)2+-based cluster driven by dimeric {Te2O6}-based templates.

Utilization of [Mo2S2O2(H2O)6]2+ and a tellurite anion led to the formation of three new clusters, 1-3, with unique structural features. The tellurite anion not only templated the formation of [(Mo2O2S2)4(TeO3)(OH)9]3-1 and [(Mo2O2S2)12(TeO3)4(TeO4)2 (OH)18]10-3, but also the in situ generation of two different types of dimeric {Te2O6} based moieties induced the spontaneous assembly of the chiral [(Mo2O2S2)10(TeO3)(Te2O6)2(OH)18]8- anionic cluster, 2.

Exploring structural complexity in the discovery and self-assembly of a family of nanoscale chalcoxides from {Se8Mo36} to {Se26Mo68}.

Herein, we show the controlled generation of multi-component libraries based on the [MoS2O2]2+/MoVIO42-/SeIVO32-/C4O42- system leading to the formation of a whole new family of nanosized molecular chalcoxides, {Se8Mo36} 1, {Se8Mo40} 2, {Se8Mo56} 3, {Se20Mo56} 4 and {Se26Mo68} 5, of the general formula {(MoO2S2)a(OH)b(SeIVO3)c(C4O4)d(MoO7)e}n-, where a, b, c, d, e, n = [16, 20, 8, 6, 2, 20] for 1, [18, 24, 8, 6, 2, 20] for 2, [24, 32, 8, 8, 4, 24] for 3, [28, 32, 20, 8, 0, 32] for 4 and [34, 36, 26, 8, 0, 36] for 5. The coordination modulation effect offered by the SeIVO32- and the C4O42- anions lead to the generation of new building blocks, [(MoO2S2)3(OH)6(C4O4) (MoO7)]4-, and the discovery of a new family of clusters of increasing nuclearity and complexity.

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.

Time-resolved assembly of cluster-in-cluster {Ag12}-in-{W76} polyoxometalates under supramolecular control.

We report the time-resolved supramolecular assembly of a series of nanoscale polyoxometalate clusters (from the same one-pot reaction) of the form: [H(10+m)Ag18Cl(Te3W38O134)2]n, where n=1 and m=0 for compound 1 (after 4 days), n=2 and m=3 for compound 2 (after 10 days), and n=∞ and m=5 for compound 3 (after 14 days). The reaction is based upon the self-organization of two {Te3W38} units around a single chloride template and the formation of a {Ag12} cluster, giving a {Ag12}-in-{W76} cluster-in-cluster in compound 1, which further aggregates to cluster compounds 2 and 3 by supramolecular Ag-POM interactions. The proposed mechanism for the formation of the clusters has been studied by ESI-MS. Further, control experiments demonstrate the crucial role that TeO3(2-), Cl(-), and Ag(+) play in the self-assembly of compounds 1-3.