Ion-pair complexes of Schiff base Fe( iii ) cations and complex anions

• Published in: New journal of chemistry Vol. 43; no. 12; pp. 4937 - 4946
• Main Authors: Nemec, Ivan, Zoufalý, Pavel, Jewula, Pawel, Antal, Peter, Linert, Wolfgang, Herchel, Radovan
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 2019
• Subjects: Anions; Cations; Crystal structure; Crystallography; Crystals; Diffraction patterns; Ethane; Imines; Ion pairs; Magnetic measurement; Magnetic permeability; Magnetic properties; Magnetism; Silver; Single crystals; X ray powder diffraction; X-ray diffraction
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/C9NJ00192A

Compound [Fe(H 2 -4OH-L 6 )]Cl was used for preparation of four new ion-pair complexes with general formula: [Fe(H 2 -4OH-L 6 )][M(L 3 ) 2 ]·H 2 O (M = Co III ( 3a ), Cr III ( 3b ) and Fe III ( 3c )) and [Fe(H 2 -4OH-L 6 )][Ag(CN) 2 ] ( 3d ), where H 4 -4OH-L 6 = N , N ′-bis[2,4-dihydroxy-(benzylideneamino)ethyl]ethane-1,2-diamine and H 2 L 3 = 2-{( E )-[(2-hydroxyphenyl)imino]methyl}phenol. Furthermore, two [Fe(H-4OH-L 6 )] complexes ( 1a and 1b ) with monodeprotonated hexadentate ligands were prepared. The crystal structures were determined by single-crystal X-ray measurements for all the above-mentioned complexes excluding 3c . Its isostructurality with 3a–b was confirmed by powder X-ray diffraction. The magnetic properties were investigated by static magnetic measurements and they are dominated by the high spin ground state of the complex cations and anions and at a smaller scale by the intermolecular interactions present among the molecules. The susceptibility and magnetization data were fitted simultaneously using the model for monomeric complexes including the zero-field splitting and the molecular field correction and these studies were supported also by CASSCF/NEVPT2 and BS-DFT calculations.