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Polyoxopalladates as Prototype Molecular Hydrogen Uptake Systems and Novel In situ Hydrogen Detectors on the Nanoscale
Author(s) -
SchmitzAntoniak Carolin,
Izarova Natalya V.,
Svechkitaliya,
Smekhova Alevtina,
Stuckart Maria,
Schmitz Detlef,
Kögerler Paul
Publication year - 2019
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.201800972
Subject(s) - chemistry , hydrogen , ion , magnetization , nanoscopic scale , oxide , absorption (acoustics) , analytical chemistry (journal) , inorganic chemistry , oxidation state , photochemistry , nanotechnology , magnetic field , organic chemistry , materials science , catalysis , physics , quantum mechanics , composite material
Dodecapalladium(II) oxide‐based molecular nanocubes encapsulating Fe 3+ (3d 5 ) or Co 2+ (3d 7 ) ions display facile hydrogen uptake with concurrent pronounced magnetization changes that suggests use as molecular hydrogen detection materials. Electronic and magnetic properties were investigated element‐specifically by X‐ray absorption spectroscopy and its associated magnetic circular and linear dichroisms. Hydrogenation reduces the Fe 3+ (3d 5 ) ions to a 3d 6 state while the Co 2+ 3d 7 configuration remains largely unaffected. However, in both cases, drastic changes of the crystal field and the magnetic properties were observed and quantified. The spin magnetic moments in the as‐prepared state were obtained to be similar to the ones expected for free ions and are reduced significantly by about 30–40 % for both Fe and Co central ions upon loading with hydrogen. In addition, re‐oxidation and hydrogenation in a second cycle were monitored and the sensitivity to hydrogen and oxygen exposure as a function of the peripheral capping groups is discussed.