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The possibility of PO(4)(3-) for MoO(4)(2-) partial substitution in the langbeinite framework has been studied by exploration of the K-Fe(Sc)-Mo(W)-P-O systems using the high-temperature solution method. It was shown that 1/3PO(4)(3-) for MoO(4)(2-) substitution leads to formation of three novel compounds K(2)Fe(MoO(4))(PO(4))(2), K(2)Sc(MoO(4))(PO(4))(2), and K(2)Sc(WO(4))(PO(4))(2) with slightly increased lattice parameters and significant distortion of the anion tetrahedra without structure changes. In contrast, the antiferromagnetic structure is modified by substitution in the low-temperature region. The structural peculiarities are discussed in light of bond-valence sums calculations.

We have studied the high spin and low spin structural phases of the two-step spin transition compound [Fe(bpp) 2 ](NCS) 2 ·2H 2 O (bpp: 2,6-bis(pyrazol-3-yl)pyridine) of different sample history with X-ray synchrotron ( λ ∼ 0.32 A) powder diffraction at different temperatures as well as with usual X-ray ( λ ∼ 1.54 A) powder diffraction at room temperature by performing rapid repeated scans at regular intervals of time. A structural phase transition occurs only during the first step of the spin transition. Time dependent interconversions of the two crystallographic phases have been observed at room temperature for this material. The results indicate that a soft X-ray (Cu-K α )-induced structural change occurs in this material at room temperature. Possible mechanisms for this unusual observation are discussed.

The spin-crossover complexes [Fe(teec)6](X)2 (with teec=1-(2-chloroethyl)-tetrazole and X=BF4, ClO4, PF6) possess two iron(II) sites each having a different spin-crossover behaviour. The magnetic behaviour of the complexes obtained by slow crystallisation differs strongly from those obtained by precipitation. This difference results in either a spin crossover of 50% (X=ClO4, crystalline), two gradual steps (X=BF4, PF6), or two steps, of which one is gradual and the other having a thermal hysteresis (X=ClO4 precipitated). Both 57Fe Mossbauer spectroscopy and magnetic susceptibility measurements have been recorded as a function of T. The crystal structure of [Fe(teec)6](BF4)2 has been determined using X-ray synchrotron powder diffraction. Of [Fe(teec)6](ClO4)2 only the cell parameters could be determined. The ligand field spectra of the low-spin and high-spin states clearly indicate a 1A1→5T2 spin transition with 10 DqLS/10 DqHS=1.72.

The passivation of low carbon steel was studied in aqueous solution of 0.5 M Na2SO4+0.001 M NaHSO3 at pH=3.5 and 6.5. The found major components at pH-3.5 were: γ-FeOOH and Fe3C, and also FeSO4.H2O could be identified on the surface of the low carbon steel as a minor component. At pH-6.5, the passive film contained only amorphous iron(III)-oxide or oxyhydroxide.

Five novel two-dimensional coordination polymers {Fe(4PhPy)(2)[M(II)(CN)(4)]}.sH(2)O (4PhyPy = 4-phenylpyridine; 1: M(II) = Pd, s = 0; 2: M(II) = Ni, s = 0; 3: M(II) = Pt, s = 1) and {Fe(4PhPy)(2)[M(I)(CN)(2)](2)}.sH(2)O (4: M(I) = Ag, s = 1; 5: M(I) = Au, s = 0.5) exhibiting spin-crossover properties have been synthesized. They were characterized at various temperatures using X-ray absorption spectroscopy (XAS), powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), and magnetic susceptibility measurements. The occurrence of a cooperative thermal spin transition detected by the magnetic method is located at critical temperatures T(c)( downward arrow)/T(c)( upward arrow) = 163 K/203 K (1), 135 K/158 K (2), and 172 K/221 K (3), and a less cooperative one is located at T(c) = 188 K (4) and 225 K (5). Compounds 1-5 show an abrupt color change from yellow (high-spin (HS) state) to red (low-spin (LS) state) upon spin-state conversion. The dehydration of the compounds changes the type of the spin transition, making it more abrupt and shifting the critical temperature to higher temperatures. For 1 and 2, XAS provides local structural information on the contraction of the FeN(6) coordination sphere upon the HS-to-LS transition, in line with the magnetic results. Variable-temperature characterization of 1 by X-ray diffraction evidences the very abrupt phase transition with a large hysteresis. A light-induced spin conversion (LIESST effect) is detected by magnetic measurements in 1-5 below 70 K.

Earlier work in our laboratory on the effect of metal dilution on the 5T2(Oh ⇌ 1A1(Oh) equilibrium in polycrystalline spin crossover systems of iron(II) has shown that the relative stability of the high spin state, 5T2(Oh), at a given temperature, increases markedly with decreasing iron concentration. These results have initiated the present work. Using 57Fe Mossbauer spectroscopy, we have investigated the electronic ground state of iron(II) in the highly diluted solid solutions [FexM1−xL3] with L = bipy, M = Mn, Ni, Zn, x ≲ 0.005 and L = phen, M = Ni, Zn, x ≲ 0.005. Although the critical field potential (Vc) of the pure iron complexes, which are known to be low spin, is reported to be not far from the crossover point Vc = P (P, the mean spin pairing energy), the effect of metal dilution does not reduce the difference ¦ Vc - P ¦ sufficiently as to thermally populate the 5T2(Oh) state at room temperature to any noticeable extent. ¦ Vc - P ¦ has been estimated to be ≳ 1200 cm−1. The quadrupole splitting and the resonance line width are nearly the same in the pure compounds and the solid solutions. The isomer shift, however, is found to increase slightly in the order M = Fe < Ni < Zn < Mn, and parallels the increase in the ionic radii of the M++ host ions.

The temperature dependent high spin (HS) ⇌ low spin (LS) transition, otherwise called spin crossover, has been well established for many first-row transition metal complexes, particularly for complexes of iron(II) [1]. The phenomenon has been observed mostly in the crystalline state, but also in solution. The spin crossover characteristics have been found to depend on various chemical influences, such as ligand substitution, the nature of the non-coordinating anion and the crystallizing solvent. It has been shown by 57Fe Mossbauer spectroscopy that the spin crossover behaviour in the solid solutions of [FexZn1−x(2-pic)3] Cl2·EtOH (2-pic = 2-picolylamine) is also susceptible to metal dilution [2, 3]. At a given temperature, the HS state becomes favoured over the LS state with decreasing x. This may be qualitatively interpreted on the grounds of a cooperative domain model [2]. A phenomenological thermodynamic treatment [4] yields estimates of the changes of enthalpy and entropy as well as the domain size. A statistical model has also been successfully applied, which also allows to estimate the domain size and, in addition, an average effective frequency of the metalligand vibrational modes in each of the two spin states. Mossbauer effect studies of the solid solution of [FexCo1−x(2-pic)3] Cl2·EtOH show similar results. The relative stability of the HS state, at a given temperature, also increases with decreasing x. The Fex/CO1−x/2-pic system, however, shows higher transition temperatures, at a given x, than the Fex/Zn1−x/2-pic system, apparently due to the more rigid lattice of the former system. The effect of metal dilution in solid solutions of [FexM1−x(phen)2(NCS)2] (M = Co, Mn, Ni) as studied by Mossbauer spectroscopy [5] follows the same line: at a given temperature, the 5T2(Oh) state becomes favoured over the 1A1(Oh) state upon lowering x.