One-Pot versus Sequential Reactions in the Self-Assembly of Gigantic Nanoscale Polyoxotungstates

Jing Gao , Jun Yan , Sebastian Beeg , De-Liang Long *, and Leroy Cronin *

By using a new type of lacunary tungstoselenite {Se2W29O103} (1), which contains a “defect” pentagonal {W(W)4} unit, we explored the assembly of clusters using this building block and demonstrate how this unit can give rise to gigantic nanomolecular species, using both a “one-pot” and “stepwise” synthetic assembly approach. Specifically, exploration of the one-pot synthetic parameter space lead to the discovery of {Co2.5(W3.5O14)(SeW9O33)(Se2W30O107)} (2), {CoWO(H2O)3(Se2W26O85)(Se3W30O107)2} (3), and {Ni2W2O2Cl(H2O)3(Se2W29O103) (Se3W30O107)2} (4), effectively demonstrating the potential of the {Se2W29} based building blocks, which was further extended by the isolation of a range of 3d transition metal doped tetramer family derivatives: {M2WnOm(H2O)m(Se2W29O102)4} (M = Mn, Co, Ni or Zn, n = 2, m = 4; M = Cu, n = 3, m = 5) (5 - 9). To contrast the ‘one-pot’ approach, an optimized stepwise self-assembly investigation utilizing 1 as a precursor was performed showing that the high nuclearity clusters can condense in a more controllable way allowing the tetrameric clusters (5 - 8) to be synthesized with higher yield, but it was also shown that 1 can be used to construct a gigantic {W174} hexameric-cluster {Cu9Cl3(H2O)18(Se2W29O102)6} (10). Further, 1 can also dimerize to {(Se2W30O105)2} (11) by addition of extra tungstate under similar conditions. All the clusters were characterized by single-crystal X-ray crystallography, chemical analysis, infrared spectroscopy, thermogravimetric analysis, and electrospray ionization mass spectrometry, which remarkably showed that all the clusters, even the largest cluster, 10 ( 50 kD), could be observed as the intact cluster demonstrating the extraordinary potential of this approach to construct robust gigantic nanoscale polyoxotungstates.