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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 107-136 
    ISSN: 0392-6737
    Keywords: Crystal and ligand fields ; Mossbauer effect ; other γ-ray spectroscopy ; Visible and ultraviolet spectra ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary Coordination compounds of transition metal ions with open-shell electron configurations may exhibit dynamic electronic-structure phenomena, depending on the nature of the coordinating ligand sphere. The change of spin state with temperature («thermal spin-crossover»), light-induced electron transfer processes leading to long-lived metastable charge and spin states (e.g., «LIESST» effect), are some of the fascinating electronic games encountered in transition metal compounds, which are presently under extensive study by chemists and physicists. Mössbauer spectroscopy plays a dominant role in the investigation of such phenomena in iron compounds, as will be demonstrated in this paper. This work will focus on selected examples of «thermal spin-crossover» in iron(II) complexes and switching between different spin states by irradiation with light of different wavelength (LIESST effect), demonstrating that Mössbauer spectroscopy besides other physical techniques proves to be a highly elegant tool for following the spin state conversion and the concomitant changes of molecular and crystal structure properties. Finally, Mössbauer emission spectroscopy, both time integral and time differential, has been employed to generate and identify long-lived excited spin states by making use of the nuclear disintegration of57Co as an intrinsic molecular light source (NIESST=nuclear decay-induced excited-spin-state trapping). Lifetime measurements by optical techniques on LIESST states and by time-differential Mössbauer coincidence spectroscopy on NIESST states prove that the relaxation pathways in the mechanisms for LIESST and NIESST are identical.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0947-6539
    Keywords: iron complexes ; magnetic susceptibility ; Mössbauer spectroscopy ; phasetransitions ; spin crossover ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The iron(II) complex [Fe(bpp)2]-(CF3SO3)2 H2O (bpp = 2,6-bis(pyrazolyl-3-yl)pyridine) shows a thermal spin transition associated with a hysteresis of approximately 140 K width. The transition temperatures T1/2 (where the fraction of HS species γHS = 0.5) are 147 K and ≍285 K in the cooling and heating directions, respectively. The compound shows the LIESST and reverse-LIESST effects at low temperatures. The relaxation of the metastable HS states generated by LIESST was observed quantitatively at temperatures between 77.5 and 85 K by Mössbauer spectroscopy. Metastable HS states can also be generated by rapid cooling of the sample. The relaxation of the metastable HS states formed by thermal spin-state trapping was monitored at temperatures between 104 and 118 K by magnetic susceptibility measurements. The relaxation mechanisms of the HS states generated by LIESST and thermal spinstate trapping are completely different. We suggest that the HS → LS relaxation after thermal spin-state trapping is triggered by an additional structural phase transition of the system.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0947-6539
    Keywords: iron complexes ; kinetics ; magnetic susceptibility ; Mössbauer spectroscopy ; spin crossover ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal and light-induced spin transitions in [Fe(bpen)(NCS)2] and [Fe(bpen)(NCSe)2] have been investigated by means of magnetic susceptibility and Mössbauer measurements. The HS → LS transition in [Fe(bpen)(NCS)2] is detected at temperatures below 120 K (T1/2 [when the fraction of high-spin species γHS = 0.5] = 68 K) with a residual HS fraction of 8% at 20 K. The transition is fairly abrupt and no hysteresis is observed, in contrast to earlier studies (ref. [8]). The generation of metastable HS states in [Fe(bpen)(NCS)2] is achieved by rapid cooling of the sample and by irradiating the compound at low temperatures with light of appropriate wavelengths (LIESST). The HS → LS relaxation of the metastable spin states after rapid cooling is observed at temperatures between 35 and 42.5 K and shows strong deviations from single exponential behavior. The spin-transition behavior changes drastically on substitution of the thiocyanate ions by NCSe-. In [Fe(bpen)(NCSe)2] a gradual and complete spin transition between 140 and 250 K is observed (T1/2 = 181 K). Irradiation of the compound with green light at low temperatures does not result in formation of long-lived metastable HS states. The spintransition curves derived from magnetic susceptibility and Mössbauer studies show good agreement for each compound, and no hints of significantly different Lamb-Mössbauer factors for the HS and LS states are observed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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