Experimental and Theoretical Identification of the Origin of Magnetic Anisotropy in Intermediate Spin Iron(III) Complexes

Lianke Wang; Matija Zlatar; Filip Vlahović; Serhiy Demeshko; Christian Philouze; Florian Molton; Marcello Gennari; Franc Meyer; Carole Duboc; Maja Gruden

doi:10.1002/chem.201705989

Experimental and Theoretical Identification of the Origin of Magnetic Anisotropy in Intermediate Spin Iron(III) Complexes

Chemistry. 2018 Apr 6;24(20):5091-5094. doi: 10.1002/chem.201705989. Epub 2018 Mar 2.

Authors

Affiliations

¹ University of Grenoble Alpes, DCM, CNRS UMR 5250, Grenoble, France.
² Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Serbia.
³ Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, 11000, Belgrade, Serbia.
⁴ Institut für Anorganische Chemie, Universität Göttingen, Tammannstr. 4, 37077, Göttingen, Germany.

Abstract

The complexes [FeL^N2S2 X] [in which L^N2S2 =2,2'-(2,2'-bipryridine-6,6'-diyl)bis(1,1'-diphenylethanethiolate) and X=Cl, Br and I], characterized crystallographically earlier and here (Fe(L)Br), reveal a square pyramidal coordinated Fe^III ion. Unusually, all three complexes have intermediate spin ground states. Susceptibility measurements, powder cw X- and Q-band EPR spectra, and zero-field powder Mössbauer spectra show that all complexes display distinct magnetic anisotropy, which has been rationalized by DFT calculations.

Keywords: density functional calculations; electronic structure; intermediate spin state; iron(III); magnetic properties.