Chemical design of heterometallic carboxylate structures with Fe3+ and Ag+ ions as a rational synthetic approach

Луценко, И. А.; Кискин, М. А.; Baravikov, Dmitry E.; Nelyubina, Yulia V.; Primakov, Petr V.; Еременко, И. Л.

doi:10.1016/j.mencom.2021.09.012

Cited by 3 publications

(1 citation statement)

References 29 publications

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“…Considering the metal coordination, the two Fe w ions have a trigonal bipyramidal ( tb ) coordination (see Figure 1 and Figure S1 in Supplementary Materials ), while usually they show an octahedral ( oh ) geometry [ 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 ]; this feature can be ascribed to the ‘strain’ induced by the Schiff base ligands. Considering the trigonal plane formed by the three oxygen atoms coordinated to Fe w , the tb polyhedra are rotated on average by 70° ( 1 ) and 84° ( 2 ) with respect to each other and by about 55° ( 1 ) and 48° ( 2 ) with respect to the Fe 4 O 2 l.s.…”

Section: Resultsmentioning

confidence: 99%

Substituent-Guided Cluster Nuclearity for Tetranuclear Iron(III) Compounds with Flat {Fe4(μ3-O)2} Butterfly Core

Marchi

Carlino

Castellano

et al. 2023

IJMS

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The tetranuclear iron(III) compounds [Fe4(μ3-O)2(μ-LZ)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 Fe4 bis-oxido clusters. All compounds show a flat almost-symmetric butterfly-like conformation of the {Fe4(μ3-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, Feb, and a pentacoordination with trigonal bipyramidal geometry for the two-wing iron ions, Few. 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 {Fe4(μ3-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.

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