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Spin-Crossover Complex (spin-crossover + complex)

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Chemistry100%

Selected Abstracts

Optical, Magnetic and Structural Properties of the Spin-Crossover Complex [Fe(btr)2(NCS)2]·H2O in the Light-Induced and Thermally Quenched Metastable States

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 36 2007
Vincent Legrand
Abstract [Fe(btr)2(NCS)2]·H2O [btr = 4,4,-bis(1,2,4-triazole)] is thearchetype of highly cooperative and low-dimensional spin-crossover complexes, which exhibit low-spin (LS) to high-spin (HS) light-induced conversion at very low temperature. The structural reorganizations related to the light-induced and thermally induced LS,HS transitions were characterized by single-crystal X-ray diffraction below the relaxation temperature (T = 15 K < TLIESST) and at 130 K within the thermal hysteresis loop. We show that the LIESST and thermal spin transitions lead to the same structural variations, namely an elongation of the Fe,N bonds by 0.18 Å (Fe,NNCS) and 0.20 Å (Fe,Nbtr), on going from LS to HS, together with a reorientation of the NCS group by nearly 13°. The atomic displacement amplitudes, derived from the crystal structures, indicate lattice vibration modes of larger amplitudes and correlatively lower vibration frequencies in the HS state. The deformation of the crystal lattice as a function of temperature and laser excitation was quantitatively analyzed in terms of the HS and LS thermal-expansion (,HS and ,LS) and spin-transition spontaneous-strain (,) tensors. The eigendirections and eigenvalues of the , and , tensors correlate well with the weak and strong interactions in the solid and are responsible for the high cooperativity and low-dimensional behaviour. Magnetic and spectroscopic measurements were performed in all the different spin states and related to the structural findings. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Two New Iron(II) Spin-Crossover Complexes with N4O2 Coordination Sphere and Spin Transition around Room Temperature

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 36 2009
Birgit Weber
Abstract The reaction of iron(II) acetate with the tetradentate Schiff base like ligand H2L1 {[3,3,]-[4,5-dihydroxy-1,2-phenylenebis(iminomethylidyne)bis(2,4-pentanedion)]} leads to the formation of the complex [FeL1(MeOH)]. Reaction of this complex with pyridine (py) or N,N,-dimethylaminopyridine (dmap) leads to the two N4O2 -coordinated complexes [FeL1(py)2]·py (1) and [FeL1(dmap)2]·MeOH·0.5dmap (2). Both complexes are spin-crossover compounds that were characterised by using magnetic measurements, X-ray crystallography and temperature-dependent 1H NMR spectroscopy. Special attention was given to the role of the two hydroxy groups on the phenyl ring in the formation of a hydrogen-bonding network and the influence of this network on the spin-transition properties. Although only a gradual spin crossover was observed for both complexes, the transition temperature was shifted to higher temperatures relative to that of the complexes with no additional hydroxy groups at the Schiff base like ligand. The hydrogen-bonding network was responsible for this effect.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

On the precision and accuracy of structural analysis of light-induced metastable states

JOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 6 2007
Vincent Legrand
Bragg diffraction data were collected on single crystals of the spin-crossover complex [Fe(phen)2(NCS)2] in its low-spin and light-induced metastable high-spin states. Experimental variables included the temperature (32 and 15,K), the X-ray source (sealed tube and synchrotron), and the time interval between laser light excitation of the sample (, = 647,nm). From a comparison of the structural parameters refined, it is shown that photo-crystallographic measurements suffer significantly and systematically from bias if the probed sample contains residual ground-state species, resulting from an incomplete photo-conversion or a significant metastable- to ground-state relaxation. It follows that a 4% population of species in a different spin state affects the Fe,N bond lengths by more than three standard deviations, and the FeN6 polyhedron volume by as much as seven standard deviations, while the mean atomic position misfit exceeds 0.005,Å. [source]

Optical, Magnetic and Structural Properties of the Spin-Crossover Complex [Fe(btr)2(NCS)2]·H2O in the Light-Induced and Thermally Quenched Metastable States

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 36 2007
Vincent Legrand
Abstract [Fe(btr)2(NCS)2]·H2O [btr = 4,4,-bis(1,2,4-triazole)] is thearchetype of highly cooperative and low-dimensional spin-crossover complexes, which exhibit low-spin (LS) to high-spin (HS) light-induced conversion at very low temperature. The structural reorganizations related to the light-induced and thermally induced LS,HS transitions were characterized by single-crystal X-ray diffraction below the relaxation temperature (T = 15 K < TLIESST) and at 130 K within the thermal hysteresis loop. We show that the LIESST and thermal spin transitions lead to the same structural variations, namely an elongation of the Fe,N bonds by 0.18 Å (Fe,NNCS) and 0.20 Å (Fe,Nbtr), on going from LS to HS, together with a reorientation of the NCS group by nearly 13°. The atomic displacement amplitudes, derived from the crystal structures, indicate lattice vibration modes of larger amplitudes and correlatively lower vibration frequencies in the HS state. The deformation of the crystal lattice as a function of temperature and laser excitation was quantitatively analyzed in terms of the HS and LS thermal-expansion (,HS and ,LS) and spin-transition spontaneous-strain (,) tensors. The eigendirections and eigenvalues of the , and , tensors correlate well with the weak and strong interactions in the solid and are responsible for the high cooperativity and low-dimensional behaviour. Magnetic and spectroscopic measurements were performed in all the different spin states and related to the structural findings. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]