A high-nuclearity {W36} isopolyoxotungstate cluster, [H12W36O120]12-, with a triangular shape has been isolated by using an encapsulating organic cation, protonated triethanolamine. In analogy to an 18-crown-6 crown ether, the cluster captures a potassium ion, present in trace amounts in the reaction system, within its cavity. DFT calculations suggest that the distribution of partial atomic charges over the oxygen framework shows maxima at certain “hotspot” sites, which imply possible routes for further cluster growth based on the {W36} system.
Cryospray mass spectrometry (CSI-MS) has been used to probe the mechanism of self-assembly of polyoxometalate clusters in solution. By using CSI-MS and electronic absorbance spectroscopy it was possible to monitor in real-time the self-assembly of polymeric chains based on [Ag 2Mo 8O 26] (2-) n building blocks. The role of the Ag (I) ion in the solution state rearrangement of molybdenum Lindqvist ({Mo 6}) into the silver-linked beta-octamolybdate ({Mo 8}) structure (( n-C 4H 9) 4N) 2 n [Ag 2Mo 8O 26] n ( 1) is revealed in unprecedented detail. A monoanionic series, in particular [AgMo m O 3 m+1 ] (-) where m = 2 to 4, and series involving mixed oxidation state polyoxomolybdate species, which illustrate the in-solution formation of the (Ag{Mo 8}Ag) building blocks, have been observed. CSI-MS detection of species with increasing metal nuclearity concomitant with increasing organic cation contribution supports the hypothesis that the organic cations used in the synthesis play an important structure-directing role in polyoxometalate (POM) growth in solution. A real-time decrease in [{Mo 6}] and associated increase in [{Mo 8}] have been observed using CSI-MS and electronic absorbance spectroscopy, and the rate of {Mo 6} interconversion to {Mo 8} was found to decrease on increasing the size of the countercation. This result can be attributed to the steric bulk of larger organic groups hindering {Mo 6} to {Mo 8} rearrangement and hindering the contact between silver cations and molybdenum anions.
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