High‐Spin Mononuclear Iron(III) Complexes with Pentadentate Schiff Base Ligands: Structural Analysis and Magnetic Properties. Issue 4 (4th April 2019)

• Record Type: Journal Article
• Authors: Pogány, Lukáš; Moncol, Ján; Pavlik, Ján; Mazúr, Milan; Šalitroš, Ivan
• Is Part Of: ChemPlusChem. Volume 84:Issue 4(2019)
• Page Start: 358
• Page End: 367
• Publication Date: 2019-04-04
• Subjects: density functional calculations -- iron(III) complexes -- magnetic properties -- N, O-ligands -- Schiff bases; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cplu.201800658
• Languages: English
• ISSNs: 2192-6506

Abstract

Abstract: Various substituted 2‐hydroxybenzophenones were combined with aliphatic linear triamines to form pentadentate Schiff base ligands. Twelve new iron(III) complexes with the general formula [Fe(L n )X]. m CH3 CN ( n =1–10; X=N3 −, NCS − or NCSe − ; m =0–2) have been synthesized, and spectrally as well as structurally characterized. The structural analysis revealed a notable dependence of coordination polyhedra deformation as well as the spatial configuration of donor atoms on the length and symmetry of the Schiff base ligands. The magnetic properties of the compounds were investigated and the permanent high‐spin state (S=5/2) for all reported compounds was established, and allowed calculation of zero‐field‐splitting parameters as well as coupling constants, which were further confirmed with DFT calculations. The solid‐state EPR spectra were recorded at 293 K and 98 K, and in accordance with the magnetic measurements, showed a high‐spin state in the measured temperature range. Abstract : Structural diversity vs .magnetism : Twelve iron(III) complexes with pentadentate Schiff bases were prepared from derivatives of 2‐hydroxybenzophenone, aliphatic triamines, and pseudohalido ligand anions. Structural investigations confirmed the expected molecular structures as well as the relationship between the length of the Schiff base ligands and configuration of the coordination polyhedra. The high‐spin‐states of the reported compounds were investigated by magnetometry, EPR spectroscopy, and DFT calculations.