Intensely Colored Mixed-Valence Iron(II) Iron(III) Formate Analogue of Prussian Blue Exhibits Neel N-Type Ferrimagnetism

The reaction of colorless iron(II) formate or the mixed-valence cluster Fe(3)O(MeCOO)(6)(H(2)O)(3) with formic acid in dimethylformamide exposed to air at 110 degrees C affords black crystals of the mixed-valence (Me(2)NH(2)) [Fe(II)Fe(III)(HCOO)(6)] three-dimensional (D) structure in which the cations occupy half of the channels. The structure consists of alternating layers of Fe(II)O(6) [Fe(1)-O(1), 2.119(1) angstrom] and Fe(III)O(6), [Fe(2)-O(2), 2.0049(9) angstrom] octahedra bridged by anti-anti-bonded formates to afford an open-framework 3D structure. The structure is very similar to those of (Me(2)NH(2))[Fe(II)(HCOO)(3)] and [Fe(III)(HCOO)(3)]center dot HCOOH, both of which are colorless. The black crystals appear dark-purple (lambda(max) = 520 nm) when powdered. The room-temperature Mossbauer spectrum confirms the 1:1 ratio of Fe(II) (delta = 1.03 mm/s, Delta E(Q) = 1.16 mm/s) and Fe(III) (delta = 0.62 mm/s, Delta E(Q) = 0.49 mm/s). Magnetic ordering that includes negative magnetization at low fields occurs at tow temperature. The only molecular-based magnetic materials in which this phenomenon has been observed are the 2D polyiron(II,III) oxalates A[Fe(II)Fe(III)(C(2)O(4))(3)] (A = R(4)N(+) cation).