Premium
Chemical and Photochemical Functionality of the First Molecular Bismuth Vanadium Oxide
Author(s) -
Tucher Johannes,
Nye Leanne C.,
IvanovicBurmazovic Ivana,
Notarnicola Antonio,
Streb Carsten
Publication year - 2012
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.201200404
Subject(s) - bismuth , vanadium , vanadium oxide , cluster (spacecraft) , photocatalysis , oxide , photochemistry , chemistry , quantum yield , metal , yield (engineering) , inorganic chemistry , visible spectrum , reactivity (psychology) , oxidation state , materials science , catalysis , organic chemistry , fluorescence , medicine , physics , alternative medicine , optoelectronics , pathology , quantum mechanics , computer science , metallurgy , programming language
Anionic metal oxide clusters, so‐called polyoxometalates, can be developed as molecular model compounds to mimic the chemical and photochemical reactivity of solid‐state metal oxides on the molecular level. Inspired by the well‐known visible‐light photocatalyst BiVO 4 , the first molecular bismuth vanadium oxide has been synthesized to investigate the chemical and photochemical similarities between the solid‐state and molecular compounds. The cluster H 3 [(Bi(dmso) 3 ) 4 V 13 O 40 ] ⋅ ca. 4 DMSO was obtained from simple precursors in almost quantitative yield. Structural analysis showed that the cluster shell is based on the unusual all‐vanadium ε‐Keggin framework [ε‐V 12 O 40 ] 15− , which is stabilized by coordination of four Bi III centers. The acidic character of the three cluster protons was demonstrated by titration studies. The cluster shows promising photocatalytic properties in visible‐light photooxidation reactions and has high activity (turnover number >1200), high quantum yield ( Φ =7.6 %), and good recyclability, which make it a promising first example of a new class of heterometallic polyoxometalates.