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Journal Article

Formation mechanism of a nano ring of bismuth cations and mono-lacunary Keggin-type phosphomolybdate


Scoppola,  Ernesto       
Wolfgang Wagermaier, Biomaterialien, Max Planck Institute of Colloids and Interfaces, Max Planck Society;

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Martins, I., Al-Sabbagh, D., Bentrup, U., Marquardt, J., Schmid, T., Scoppola, E., et al. (2022). Formation mechanism of a nano ring of bismuth cations and mono-lacunary Keggin-type phosphomolybdate. Chemistry – A European Journal, 28(27): e202200079. doi:10.1002/chem.202200079.

Cite as: https://hdl.handle.net/21.11116/0000-000A-1DC0-D
A new hetero-bimetallic polyoxometalate (POM) nano ring was synthesized in a one-pot procedure. The structure consists of tetrameric units containing four bismuth-substituted monolacunary Keggin anions including distorted [BiO8] cubes. The nano ring is formed via self -assembly from metal precursors in aqueous acidic medium. The compound (NH4)16[(BiPMo11O39)4]×22H2O; (P4Bi4Mo44) was characterized by single-crystal X-ray diffraction, extended X-ray absorption fine structure spectroscopy (EXAFS), Raman spectroscopy, matrix-assisted laser desorption/ionisation-time of flight mass spectrometry (MALDI-TOF), and thermogravimetry/differential scanning calorimetry (TG-DSC-MS). The formation of the nano ring in solution was studied by time-resolved in situ small- and wide-angle X-ray scattering (SAXS/WAXS) and in situ EXAFS measurements at the Mo-K and the Bi-L3 edge indicating a two-step process consisting of condensation of Mo-anions and formation of Bi-Mo-units followed by a rapid self-assembly to yield the final tetrameric ring structure.