Mossbauer Studies of Some Iron
Abstract
^{57}Fe Mossbauer spectroscopy was used to investigate several iron(III) spin crossover systems as well as a cold cholesteric liquid crystal. Tris thioseleno- and tris diselenocarbamates were found to be similar to their corresponding tris monothio and tris dithio complexes, showing increasing magnetic moment with increasing isomer shift and decreasing magnetic moment with increasing quadrupole splitting. These observations indicate that the tris thioseleno- and tris diselenocarbamates are, like their dithio analogs, spin crossover systems. Several mixed ligand thioseleno complexes were also studied and found to be similar to the corresponding dithio complexes. A possible trihydrate of Fe(S_2CN(CH _2CH_2OH) _2)_3 was investigated. Repeated attempts to reproduce a recently published four line Mossbauer spectrum for the trihydrate failed. It was concluded that the published methods actually result in the anhydrous complex. Heating of this complex in accordance with the published methods to produce the anhydrous complex resulted in decomposition. Anhydrous preparations of Fe(S_2CN(CH _2CH_2OH) _2)_3 when recrystallized from methanol without heating produced four line Mossbauer spectra at low temperatures. The temperature dependencies of the isomer shift, quadrupole splitting, and peak area indicate that, in this case, the interconversion rate between the two spin states has slowed to below the inverse of the Mossbauer time scale. This slowing is believed to be caused by partial solvation by small, nonstoichiometric, quantities of methanol. Cholesterol-2-(2-ethoxy ethoxy) ethyl carbonate was investigated via Mossbauer spectroscopy by dissolving into it 0.16wt% ^{57 }Fe enriched 1,1^' -diacetylferrocene. A glass transition temperature of 177 K and a Mossbauer Debye temperature of 32.7 K were measured. An increase in the average half width of the resonance lines above the glass transition temperature indicates the onset of diffusion in the supercooled liquid. A lack of change in the quadrupole splitting suggests that this diffusion is translational rather than rotational.
- Publication:
-
Ph.D. Thesis
- Pub Date:
- 1991
- Bibcode:
- 1991PhDT.......118B
- Keywords:
-
- III) SPIN CROSSOVER SYSTEMS AND A COLD CHOLESTERIC LIQUID CRYSTAL (GLASS;
- DITHIOCARBAMATES;
- Physics: Condensed Matter; Physics: General