Filtern
Dokumenttyp
- Zeitschriftenartikel (2) (entfernen)
Sprache
- Englisch (2)
Schlagworte
- Polyoxometalates (2) (entfernen)
Organisationseinheit der BAM
Formation Mechanism of a Nano-Ring of Bismuth Cations and Mono-Lacunary Keggin-Type Phosphomolybdate
(2022)
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] ⋅ 22 H2O; (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 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−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.
The syntheses, crystal structures, and physical properties of [HFe19O14(OEt)30] and {Fe11(OEt)24}1 are reported. [HFe19O14(OEt)30] has an octahedral shape. Its core with a central Fe metal ion surrounded by six m6-oxo ligands is arranged in the rock salt structure. {Fe11(OEt)24}1 is a mixedvalence coordination polymer in which FeIII metal ions form three 3D interpenetrating (10,3)-b nets. The arrangement of the FeIII ions can also be compared to that of Si ions in a-ThSi2. Thus, the described structures are at the interface between molecular and solid-state chemistry.