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Magnetic Anisotropy of Cr(III) Ions in Polymeric Oxalate Complexes as Revealed by HF-ESR Spectroscopy

Abstract

Two new Cr(III) paramagnetic polymeric complexes: {[CaCr2(phen)2(C2O4)4]·0.33H2O} n (CrPhen) and {[CaCr2(bpy)2(C2O4)4]·0.83H2O} n (CrBpy), where phen = 1,10-phenanthroline and bpy = 2,2\('\)-bipyridine, have been studied by high-field high-frequency electron spin resonance (HF-ESR) spectroscopy. From the oriented powder spectra, recorded in the frequency range 83–332 GHz in magnetic fields up to 16 T, the spin-Hamiltonian parameters, \(g\), \(D\) and \(E\), have been obtained. Both chromium complexes have a small negative (easy axis) magnetic anisotropy \(|D|<1\) K. CrPhen complex is biaxial, i.e., besides axial \(D\), there is also significant rhombic zero-field splitting (ZFS) parameter, \(E\). Contrary to CrPhen, CrBpy complex is uniaxial, but described by two sets of axial ZFS parameters. Despite very similar crystallographic structures of both complexes, HF-ESR spectroscopy resolved the existence of two magnetically inequivalent Cr(III) ions in CrBpy complex. The results fully support the earlier X-ray, SQUID magnetization and powder X-band ESR studies.

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Acknowledgments

This research was supported in part by the Ministry of Science, Education and Sports of the Republic of Croatia (Projects 098-0982915-2939 and 098-0982904-2946). The work was supported in part by the Deutsche Forschungsgemeinschaft through FOR1154 “Towards Molecular Spintronics”. The work of D. Žilić at the IFW Dresden was realized through the Croatian Science Foundation (HRZZ) postdoc scholarship (Project 02.03/164).

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Correspondence to Dijana Žilić.

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Žilić, D., Androš, L., Krupskaya, Y. et al. Magnetic Anisotropy of Cr(III) Ions in Polymeric Oxalate Complexes as Revealed by HF-ESR Spectroscopy. Appl Magn Reson 46, 309–321 (2015). https://doi.org/10.1007/s00723-014-0630-7

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Keywords

  • Electron Spin Resonance
  • Electron Spin Resonance Spectrum
  • Magnetic Anisotropy
  • Electron Spin Resonance Line
  • Resonance Branch