A proof of principle study is reported which introduces a new synthetic route for the assembly of 1-dimensional barium-linked polyoxovanadate chains. Bulky coordinating solvents featuring a binding site and a blocking site are employed and allow the controlled linkage of decavanadate clusters, [V10O28]6−, by barium(II) centres. Using the bulky solvent N-methyl-2-pyrrolidone (NMP), it is shown that a complex supramolecular architecture, {[Ba(nmp)4(H2O)]2[H4V10O28]}{[Ba(nmp)3(H2O)2][H3V10O28]}2·2H2O·10 NMP}∞ (1) can be accessed where mono- and dinuclear barium units link decavanadate clusters into a linear chain. Using N,N-dimethyl formamide (DMF), a less complex architecture, [(Ba(dmf)4]2[H2V10O28] (2), is formed where only dinuclear barium(II) linkages are observed. Theoretical Hirshfeld-analysis of the crystal lattices is used to examine the ‘shielding’ effect of the bulky ligands. ESI-mass-spectrometric studies give insight into potential fragments formed in solutions of 1 and 2.
