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A Mixed‐Addenda Mo/W Organofunctionalised Hybrid Polyoxometalate
Author(s) -
Amin Sharad S.,
Cameron Jamie M.,
Winslow Max,
Davies E. Stephen,
Argent Stephen P.,
Robinson David,
Newton Graham N.
Publication year - 2022
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202200019
Subject(s) - polyoxometalate , chemistry , crystallography , lacunary function , cyclic voltammetry , cluster (spacecraft) , electron paramagnetic resonance , density functional theory , homo/lumo , single crystal , paramagnetism , electrochemistry , molecule , computational chemistry , nuclear magnetic resonance , organic chemistry , catalysis , physics , mathematics , electrode , quantum mechanics , computer science , pure mathematics , programming language
A mixed‐addenda W/Mo hybrid polyoxometalate cluster – K 6 [P 2 W 15 Mo 2 O 61 (POC 6 H 5 ) 2 ] ( 1 ) was synthesised from the condensation of K 10 [P 2 W 15 Mo 2 O 61 ] and PO 3 C 6 H 7 under acidic conditions. Single‐crystal X‐ray diffraction confirmed the structure of the hybrid cluster and the presence of two Mo centres in the cap of the lacunary cluster. The electronic effects of metal substitution were studied by cyclic voltammetry, spectroelectrochemistry and electron paramagnetic resonance spectroscopy and supported by density functional theory calculations. Comparing 1 to its tungsten‐only analogue K 6 [P 2 W 17 O 61 (POC 6 H 5 ) 2 ] ( 2 ), a more positive potential for the first reduction process was induced by the substitution of W for Mo, consistent with a significant lowering of the cluster LUMO energy.