Reaction Pathway to the Only Open-Shell Transition-Metal Keggin Ion without Organic Ligation: Reaction Pathway to the Only Open-Shell Transition-Metal Keggin Ion without Organic Ligation

Wang, Wei; Amiri, Mehran; Kozma, Karoly; Lu, Jian; Zakharov, Lev N.; Nyman, May

doi:10.1002/ejic.201801087

Reaction Pathway to the Only Open-Shell Transition-Metal Keggin Ion without Organic Ligation: Reaction Pathway to the Only Open-Shell Transition-Metal Keggin Ion without Organic Ligation

Journal Article · Fri Oct 26 04:00:00 EDT 2018 · European Journal of Inorganic Chemistry

DOI:https://doi.org/10.1002/ejic.201801087· OSTI ID:1611516

^[1]; Amiri, Mehran ^[2]; ^[2]; Lu, Jian ^[3]; ^[2]; ^[2]

Chinese Academy of Sciences (CAS), Shanghai (China). Fujian Institute of Research on the Structure of Matter, Key Laboratory of Optoelectronic Materials Chemistry and Physics; DOE/OSTI
Oregon State Univ., Corvallis, OR (United States)
Chinese Academy of Sciences (CAS), Shanghai (China). Fujian Institute of Research on the Structure of Matter, Key Laboratory of Optoelectronic Materials Chemistry and Physics

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 Cr³⁺ 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.

View Accepted Manuscript (DOE)

Research Organization:: Oregon State University, Corvallis, OR (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0010802

OSTI ID:: 1611516

Alternate ID(s):: OSTI ID: 1479159

Journal Information:: European Journal of Inorganic Chemistry, Journal Name: European Journal of Inorganic Chemistry Journal Issue: 42 Vol. 2018; ISSN 1434-1948

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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