The dimeric [V{sub 2}O{sub 2}F{sub 8}]{sup 4−} anion: Structural characterization of a magnetic basic-building-unit

Journal Article · Mon Apr 15 04:00:00 EDT 2013 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/J.JSSC.2013.01.021· OSTI ID:22304539

Lu, Hongcheng ^[1]; Gautier, Romain ^[1]; Li, Zuo-Xi ^[2]; Jie, Wanqi ^[2]; Liu, Zhengtang ^[2]

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1. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208 (United States)
2. State Key Laboratory of Solidification Processing, School of Material Science and Engineering, Northwestern Polytechnical University, 127 Youyixilu Road, Xi'an 710072 (China)

New materials built from the [V{sub 2}O{sub 2}F{sub 8}]{sup 4−} anionic basic-building-unit (BBU) exhibit interesting magnetic properties owing to the proximity of the two d{sup 1} V(IV) cations and the orbital interactions of fluoride and oxide ligands. In our search to target such materials, the vanadium oxide–fluoride compound [dpaH{sub 2}]{sub 2}[V{sub 2}O{sub 2}F{sub 8}] in which a dimeric anion [V{sub 2}O{sub 2}F{sub 8}]{sup 4−} is isolated in a hydrogen bond network was hydrothermally synthesized (dpa=2,2′-dipyridylamine). This hydrogen bond network is able to stabilize the highly ionic species [V{sub 2}O{sub 2}F{sub 8}]{sup 4−} as demonstrated with bond valence calculations. The coordination of the O{sup 2−}/F{sup −} ordered ligands was investigated and antiferromagnetic coupling of the isolated BBU was measured. - The new hybrid compound [dpaH{sub 2}]{sub 2}[V{sub 2}O{sub 2}F{sub 8}] built from the interesting [V{sub 2}O{sub 2}F{sub 8}]{sup 4−} magnetic basic-building-unit (BBU) was synthesized by the hydrothermal method. The coordination of the O{sup 2−}/F{sup −} ordered ligands was investigated by BVS calculations and antiferromagnetic coupling was measured. Highlights: ► A new vanadium oxyfluoride was synthesized by hydrothermal method. ► The Dimeric [V{sub 2}O{sub 2}F{sub 8}]{sup 4−} basic building unit is isolated in the hydrogen bond networks. ► The coordination of [V{sub 2}O{sub 2}F{sub 8}]{sup 4−} units to the extended structure is investigated. ► Isolated [V{sub 2}O{sub 2}F{sub 8}]{sup 4−} units exhibit antiferromagnetic coupling.

• OSTI ID: 22304539
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Vol. 200; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ANIONS
ANTIFERROMAGNETISM
CATIONS
COUPLING
HYDROGEN
HYDROTHERMAL SYNTHESIS
INTERACTIONS
LIGANDS
MAGNETIC PROPERTIES
OXYFLUORIDES
VANADATES
VANADIUM
VANADIUM OXIDES