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Abstract
Binuclear Iron(III) complexes with salten or salen ligands [Fe2(salten)2(t-L)](BPh4)2 and [Fe2(salen)2(t-L)(L′)2](ClO4)2 (L1 = azobis(4-pyridine) and L2 = 4,4′(-vinylenebis(pyridine)) were prepared and characterized by Mössbauer spectra and magnetic susceptibilities. The crystal structures of [Fe2 (salten)2(t-L1](BPh4)2 (1), [Fe2(salten)2(t-L2)](BPh4)2 (2) and [Fe2(salen)2(t-L2)(H2O)2](ClO4)2·(t-L2)·H2O (3) were determined. Crystal data for 1 : C98H94O4N10B2Fe2, space group P2l/c, Z=2, a=16.422(7), b=16.005(6), c=16.565(8) Å, β=108.47(3)°, V=4129(2) Å3, R=0.075, Rw =0.060. Crystal data for 2 : C100H96O4N8B2Fe2, space group P2l/a, Z=2, a=16.554(8), b=15.877(3), c=16.823(3) Å, β=109.20(2)°, V=4175(1) Å3, R=0.051, Rw =0.040. Crystal data for 3: C52H52O16N12Cl2Fe2, space group P 1, Z=1, a=11.744(4), b=15.710(5), c=8.177(2) Å, α=94.60(3)°, β=90.29(3)°, γ=110.84(2)°, V=4129(2) Å3, R=0.075, Rw =0.060. The complex [Fe2(salen)2(t-L2)(im)2](BPh4)2·3H2O (4) was prepared to compare with the complex 3. The complexes 1 and 2 exhibited spin-crossover behavior depending on temperature, interexchange the rates of which are rapid compared to the Mössbauer time scale (107/s). The complex 3 was in the high-spin state and the complex 4 was mixture of the high-spin and low-spin species.
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