Unexpected hydrolytic transformation of new type hybrid bromobismuthates with methylpyrazinium dications

A series of new type hybrid bromobismuthates formed by various pyrazinium cations were isolated and studied. In the systems initially containing iodide anions and monocations of substituted pyrazines, the complexes based on doubly charged cations of substituted pyrazines instead of ones based on the corresponding monocations were surprisingly formed. The variation of substituted pyrazinium cations affects not only the crystal structures of hybrid bromobismuthates via tuning the nuclearity of the anions but also the hydrolytic stability of the compounds. A thorough structural study of hydrolytic transformations was performed for halobismuthates for the first time. The results revealed a stepwise course of the process affording several products. Spectral studies of the complexes evidence that the values of optical band gaps (E_g) are low in comparison with those for similar systems which is most likely due to the cooperative effect involving the nature of the corresponding cations together with the features of the supramolecular structures of the complexes.