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

Abstract

The complexes [FeLN2S2X] [in which LN2S2=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 FeIII 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.