Substituent-Guided Cluster Nuclearity for Tetranuclear Iron(III) Compounds with Flat {Fe4(μ3-O)2} Butterfly Core
Articolo
Data di Pubblicazione:
2023
Citazione:
Substituent-Guided Cluster Nuclearity for Tetranuclear Iron(III) Compounds with Flat {Fe4(μ3-O)2} Butterfly Core / L. Marchi, S. Carlino, C. Castellano, F. Demartin, A. Forni, A.M. Ferretti, A. Ponti, A. Pasini, L. Rigamonti. - In: INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES. - ISSN 1422-0067. - 24:6(2023 Mar 18), pp. 5808.1-5808.15. [10.3390/ijms24065808]
Abstract:
The tetranuclear iron(III) compounds [Fe-4(mu(3)-O)(2)(mu-L-Z)(4)] (1-3) were obtained by reaction of FeCl3 with the shortened salen-type N2O2 tetradentate Schiff bases N,N'-bis(salicylidene)-o-Z-phenylmethanediamine H2LZ (Z = NO2, Cl and OMe, respectively), where the one-carbon bridge between the two iminic nitrogen donor atoms guide preferentially to the formation of oligonuclear species, and the ortho position of the substituent Z on the central phenyl ring selectively drives towards Fe-4 bis-oxido clusters. All compounds show a flat almost-symmetric butterfly-like conformation of the {Fe-4(mu(3)-O)(2)} core, surrounded by the four Schiff base ligands, as depicted by both the X-ray molecular structures of 1 and 2 and the optimized geometries of all derivatives as obtained by UM06/6-311G(d) DFT calculations. The strength of the antiferromagnetic exchange coupling constants between the iron(III) ions varies among the three derivatives, despite their magnetic cores remain structurally almost unvaried, as well as the coordination of the metal ions, with a distorted octahedral environment for the two-body iron ions, Fe-b, and a pentacoordination with trigonal bipyramidal geometry for the two-wing iron ions, Fe-w. The different magnetic behavior within the series of examined compounds may be ascribed to the influence of the electronic features of Z on the electron density distribution (EDD) of the central {Fe-4(mu(3)-O)(2)} core, substantiated by a Quantum Theory of Atoms In Molecules (QTAIM) topological analysis of the EDD, as obtained by UM06 calculations 1-3.
Tipologia IRIS:
01 - Articolo su periodico
Keywords:
DFT calculations; Schiff bases; X-ray structures; halogen bond; magnetic properties; oligonuclear complexes; tetradentate ligands
Elenco autori:
L. Marchi, S. Carlino, C. Castellano, F. Demartin, A. Forni, A.M. Ferretti, A. Ponti, A. Pasini, L. Rigamonti
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