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

The complexes [(FeLX)-X-N2S2] [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 Mossbauer 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

Source:
Chemistry-A European Journal, 2018, 24, 20, 5091-5094

Publisher:

Wiley-V C H Verlag Gmbh, Weinheim

Projects:

Rational design and synthesis of biologically active and coordination compounds and functional materials, relevant for (bio)nanotechnology (RS-172035)
COST Action ECOSTBio (Explicit Control Over Spin-States in Technology and Biochemistry) including a STSM grant [CM1305, COST-STSM-CM1305-25068]
China Scholarship Council
Deutsche Forschungsgemeinschaft (collaborative DFG/ANR project) [Me1313/14-1]
Serbian-French collaboration project [451-03-39/2016-09/06, 36224WB, ANR-11-LABX-003]