Abstract
We have studied the temperature-dependent Mössbauer spectra of polycrystalline samples of several five-coordinate Fe(II)-NO model compounds: octaethylporphyrin (OEP), tetraphenylporphyrin (TPP), tetramesitylporphyrin (TMP), and tetratolylporphyrin (TTP). The OEP model shows a single symmetric quadrupole doublet, while for all the other species, the quadrupole double is asymmetric, with the lower-velocity line significantly broadened. X-ray structure determinations of Fe(TPP)NO show significant disorder of the Fe-N-O plane, and we believe the broadened Mössbauer spectra also reflect this disorder. Data on OEP and TPP at 4.2K in fields of 4T and 9T are fit well by a paramagnetic S=l/2 model. While the temperature variation of the quadrupole splitting and isomer shift values for these species is weak, the compounds exhibit an unusually rapid drop in absorption area with temperature, consistent with Debye temperatures of 81K(OEP), 64K(TMP), 55K(TPP) and 47K(TTP).
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Schulz, C.E., Wyllie, G.R.A., Scheidt, W.R. (2002). Mössbauer Studies of Fe(II)-nitrosyl Porphyrin Model Compounds. In: Thomas, M.F., Williams, J.M., Gibb, T.C. (eds) Hyperfine Interactions (C). Springer, Dordrecht. https://doi.org/10.1007/978-94-010-0281-3_80
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DOI: https://doi.org/10.1007/978-94-010-0281-3_80
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