Abstract
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 [BiO(8) ] cubes. The nano-ring is formed via self-assembly from metal precursors in aqueous acidic medium. The compound (NH(4) )(16) [(BiPMo(11) O(39) )(4) ] ⋅ 22 H(2) O; (P(4) Bi(4) Mo(44) ) 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 mass spectrometry (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-L(3) 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.