title: Nb2O2F3: a reduced niobium (III/IV) oxyfluoride with a complex structural, magnetic, and electronic phase transition.
abstract: A new niobium oxyfluoride, Nb2O2F3, synthesized through the reaction of Nb, SnO, and SnF2 in Sn flux, within welded Nb containers, crystallizes in a monoclinic structure (space group: I2/a; a = 5.7048(1)Å, b = 5.1610(1)Å, c = 12.2285(2)Å, β = 95.751(1)°). It features [Nb2X10] units (X = O, F), with short (2.5739(1) Å) Nb-Nb bonds, that are linked through shared O/F vertices to form a 3D structure configurationally isotypic to ζ-Nb2O5. Nb2O2F3 undergoes a structural transition at ∼90 K to a triclinic structure (space group: P1̅; a = 5.1791(5)Å, b = 5.7043(6)Å, c = 6.8911(7)Å, α = 108.669(3)°, β = 109.922(2)°, γ = 90.332(3)°). The transition is described as a disproportionation or charge ordering of [Nb2](7+) dimers: (2[Nb2](7+) → [Nb2](6+) + [Nb2](8+)), resulting in doubly (2.5000(9) Å) and singly bonded (2.6560(9) Å) Nb2 dimers. The structural transition is accompanied by an unusual field-independent "spin-gap-like" magnetic transition.
authors.affiliation: Department of Chemistry, ‡Department of Physics, and §Texas Center for Superconductivity, University of Houston , Houston, Texas 77204, United States.
authors.forename: T Thao
authors.initials: TT
authors.lastname: Tran
authors.forename: Melissa
authors.initials: M
authors.lastname: Gooch
authors.forename: Bernd
authors.initials: B
authors.lastname: Lorenz
authors.forename: Alexander P
authors.initials: AP
authors.lastname: Litvinchuk
authors.forename: Maurice G
authors.initials: MG
authors.lastname: Sorolla
authors.forename: Jakoah
authors.initials: J
authors.lastname: Brgoch
authors.forename: Paul C W
authors.initials: PC
authors.lastname: Chu
authors.forename: Arnold M
authors.initials: AM
authors.lastname: Guloy