By using a new type of lacunary tungstoselenite {Se(2)W(29)O(103)} (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 {Co(2.5)(W(3.5)O(14))(SeW(9)O(33))(Se(2)W(30)O(107))} (2), {CoWO(H(2)O)(3)(Se(2)W(26)O(85))(Se(3)W(30)O(107))(2)} (3), and {Ni(2)W(2)O(2)Cl(H(2)O)(3)(Se(2)W(29)O(103)) (Se(3)W(30)O(107))(2)} (4), effectively demonstrating the potential of the {Se(2)W(29)} based building blocks, which was further extended by the isolation of a range of 3d transition metal doped tetramer family derivatives: {M(2)W(n)O(m)(H(2)O)(m)(Se(2)W(29)O(102))(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 {W(174)} hexameric-cluster {Cu(9)Cl(3)(H(2)O)(18)(Se(2)W(29)O(102))(6)} (10). Further, 1 can also dimerize to {(Se(2)W(30)O(105))(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.
