Abstract
A combination of density functional theory (DFT) calculations and Mössbauer spectroscopy has been used to determine that the magnetic easy-axis is coincident with its crystallography c-axis in [Fe(pca) 2(py)2] · py, where pac is the 2- pyrazinecarboxylate ligand. This easy-axis bisects the approximately axial O-Fe-O coordination axes of molecules adjacent to each other along the c-axis. in {[Fe(pca)2(H2O)]-H2O) n the easy magnetic axis is not coincident with any of its crystallographic axes nor with the Fe-O(water) coordination axis, but is coincident with one of the Fe ... Fe axes in the crystal structure. the DFT calculations, which use the B3LYP functional and the 6-311+ +G(d,p) basis set, yield s-electron probability densities and electric field gradient tensors for the iron(II) ion that are in excellent agreement with the observed iron-57 Mössbauer spectral isomer shifts and quadrupole interactions. the gas phase results are very similar for calculations based either on the X-ray structures of the two complexes or on their optimized structures; the optimized structures indicate that the iron to ligand bond distances increase in the absence of any solid-state lattice interactions. the results of a normal coordinate vibrational mode analysis of the two optimized structures are compared with the observed infrared spectra © 2009 American Chemical Society.
Recommended Citation
G. J. Long et al., "Combined Mössbauer Spectral and Density Functional Theory Determination of the Magnetic Easy-axis in Two High-spin Iron(II) 2-pyrazinecarboxylate Complexes," Inorganic Chemistry, vol. 48, no. 17, pp. 8173 - 8179, American Chemical Society, Sep 2009.
The definitive version is available at https://doi.org/10.1021/ic9003609
Department(s)
Chemistry
International Standard Serial Number (ISSN)
0020-1669
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2024 American Chemical Society, All rights reserved.
Publication Date
07 Sep 2009
PubMed ID
19630378
