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Formation Mechanism of a Nano‐Ring of Bismuth Cations and Mono‐Lacunary Keggin‐Type Phosphomolybdate
Author(s) -
Martins Inês C. B.,
AlSabbagh Dominik,
Bentrup Ursula,
Marquardt Julien,
Schmid Thomas,
Scoppola Ernesto,
Kraus Werner,
Stawski Tomasz M.,
Guilherme Buzanich Ana,
Yusenko Kirill V.,
Weidner Steffen,
Emmerling Franziska
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202200079
Subject(s) - polyoxometalate , extended x ray absorption fine structure , chemistry , crystallography , desorption , mass spectrometry , bismuth , thermogravimetry , differential scanning calorimetry , analytical chemistry (journal) , absorption spectroscopy , inorganic chemistry , organic chemistry , adsorption , physics , quantum mechanics , chromatography , thermodynamics , catalysis
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.