One- and two-step spin-crossover behavior of [FeII(isoxazole )6]2+ and the structure and magnetic properties of triangular [FeIII3O(OAc)6(isoxazole)3][ClO4]

被引:78
作者
Hibbs, W [1 ]
van Koningsbruggen, PJ [1 ]
Arif, AM [1 ]
Shum, WW [1 ]
Miller, JS [1 ]
机构
[1] Univ Utah, Dept Chem, Salt Lake City, UT 84112 USA
关键词
D O I
10.1021/ic034226p
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The structure and spin-crossover magnetic behavior of [Fe II16][BF4]2 (1 = isoxazole) and [FeII16][ClO4]2 have been studied. [FeII16][BF4]2 undergoes two reversible spin-crossover transitions at 91 and 192 K, and is the first two-step spin transition to undergo a simultaneous crystallographic phase transition, but does not exhibit thermal hysteresis. The single-crystal structure determinations at 260 [space group P3̄, a = 17.4387(4) Å, c = 7.6847(2) Å] and at 130 K [space group P1̄, a = 17.0901(2) Å, b = 16.7481(2) Å, c = 7.5413(1) Å, α = 90.5309(6)°, β = 91.5231(6)°, γ = 117.8195(8)°] reveal two different iron sites, Fe1 and Fe2, in a 1:2 ratio. The room-temperature magnetic moment of 5.0 μB is consistent with high-spin Fe(II). A plateau in μ(T) having a moment of 3.3 μB centered at 130 K suggests a mixed spin system of some high-spin and some low-spin Fe(II) molecules. On the basis of the Fe-N bond distances at the two temperatures, and the molar fraction of high-spin molecules at the transition plateau, Fe1 and Fe2 can be assigned to the 91 and 192 K transitions, respectively. [Fe II16][ClO4]2 [space group P3̄, a = 17.5829(3) Å, c = 7.8043(2) Å, β = 109.820 (3)°, T = 295 K] also possesses Fe1:Fe2 in a 1:2 ratio, and magnetic measurements show a single spin transition at 213 K, indicating that both Fe1 and Fe2 undergo a simultaneous spin transition. [FeII16][ClO 4]2 slowly decomposes in solutions containing acetic anhydride to form [FeIII3O(OAc)61 3][ClO4] [space group l2, a = 10.1547(7) Å, b = 16.5497(11) Å, c = 10.3205(9) Å, β = 109.820 (3)°, T = 200 K]. The isosceles Fe3 unit contains two Fe⋯Fe distances of 3.2844(1) Å and a third Fe⋯Fe distance of 3.2857(1) Å. The magnetic data can be fit to a trinuclear model with ℋ = -2J(S 1·S2 + S2·S3) - 2J13(S1·S3), where J = -27.1 and J 13 = -32.5 cm-1.
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页码:5645 / 5653
页数:9
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