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Reaction Pathway to the Only Open‐Shell Transition‐Metal Keggin Ion without Organic Ligation
Author(s) -
Wang Wei,
Amiri Mehran,
Kozma Karoly,
Lu Jian,
Zakharov Lev N.,
Nyman May
Publication year - 2018
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.201801087
Subject(s) - chemistry , electrospray ionization , aqueous solution , reactivity (psychology) , transition metal , open shell , mass spectrometry , organic synthesis , combinatorial chemistry , inorganic chemistry , ion , organic chemistry , catalysis , medicine , alternative medicine , pathology , chromatography
Aqueous metal‐oxo clusters without organic ligands (including polyoxometalates and group 13 polycations) are useful for energy, environmental and biomolecular applications. While ligands stabilize clusters of different elements, such as open‐shell transition metals, they inhibit reactivity and solubility. Therefore a grand challenge is to conceive and execute synthetic strategies to isolate metal‐oxo clusters of any composition, without ligation. Here we crystallize and structurally characterize a Cr 3+ dodecamer Keggin ion without organic ligation. Detailed characterization of its formation leads to understanding its reaction pathway, which may translate to isolation of other open‐shell transition metal‐oxo clusters. We employed electrospray ionization mass spectrometry, Raman spectroscopy and X‐ray scattering (small‐angle and total) to identify important reaction intermediates and processes. The aqueous synthesis presented here is simple to implement and scalable, producing pure phase materials in gram quantities.