Spontaneous formation of a chiral (MoOS)-based cluster driven by dimeric {TeO}-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 {SeMo} to {SeMo}.

Herein, we show the controlled generation of multi-component libraries based on the [MoSO]/MoO/SeO/CO system leading to the formation of a whole new family of nanosized molecular chalcoxides, {SeMo} 1, {SeMo} 2, {SeMo} 3, {SeMo} 4 and {SeMo} 5, of the general formula {(MoOS)(OH)(SeO)(CO)(MoO)}, 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 SeO and the CO anions lead to the generation of new building blocks, [(MoOS)(OH)(CO) (MoO)], 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 (Mo O S ).

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 O S (H O) ] cation with the general formula (NMe ) K [(Mo O S ) (TeO ) (C O ) (OH) ] where a,b,c,d,e,f={1,7,14,2,4,10}=1, {Mo Te }; {2,26,36,12,10,48}=2, {Mo Te }; {0,11,15,3,3,21}=3, {Mo Te }; {2,6,12,2,4,16}=4, {Mo Te }. 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 Te } to the stacked ring structure of {Mo Te }, which is the largest tellurium-containing POTM cluster reported so far.

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.