Ferrimagnetic Mixed-Valency and Mixed-Metal Tris(oxalato)iron(III) Compounds: Synthesis, Structure, and Magnetism.

The synthesis and structural and magnetic characterization of 16 compounds AM(II)Fe(III)(C(2)O(4))(3) (A = N(n-C(3)H(7))(4), N(n-C(4)H(9))(4), N(n-C(5)H(11))(4), P(n-C(4)H(9))(4), P(C(6)H(5))(4), N(n-C(4)H(9))(3)(C(6)H(5)CH(2)), (C(6)H(5))(3)PNP(C(6)H(5))(3), As(C(6)H(5))(4); M(II) = Mn, Fe) are reported. X-ray powder diffraction profiles are indexed in R3c or its subgroup P6(5)22 or P6/mmm to derive unit cell constants. The structures of all the compounds consist of two-dimensional honeycomb networks [M(II)Fe(III)(C(2)O(4))(3)(-)](infinity). The M(II) = Fe compounds behave as ferrimagnets with T(c) between 33 and 48 K, but five exhibit a crossover from positive to negative magnetization near 30 K when cooled in a field of 10 mT. The compounds exhibiting this unusual magnetic behavior are those that have the highest T(c). Within the set N(n-C(n)()H(2)(n)()(+1))(4)Fe(II)Fe(III)(C(2)O(4))(3) (n = 3-5), T(c) increases with interlayer separation and the low-temperature magnetization changes from positive (n = 3) to negative (n = 4, 5). In the M = Mn(II) compounds, the in-plane cell parameter a(0) is approximately 0.03 Å greater than in the corresponding M = Fe(II) ones while the interlayer separation (c(0)/6) is on average 0.08 Å smaller. All members of the M(II) = Mn series have magnetic susceptibilities showing broad maxima at 55 K characteristic of two-dimensional antiferromagnetism, but the magnetization of several of the salts increases sharply below 27 K due to the onset of spin canting, the magnitude of which varies significantly with A.