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- W2052524378 abstract "A series of four high-spin ferrous complexes of polydentate Schiff base ligands has been prepared and studied with IR, X-ray absorption and Mössbauer spectroscopy and variable-temperature magnetic susceptibility. The ligands include potentially tridentate and hexadentate Schiff bases with N2O and N4O2 donor sets, respectively, and result from the condensation of 5-nitrosalicylaldehyde with 2- (aminoethyl)pyridine or tetramines. The results obtained provide evidence that the four complexes described herein are mononuclear high-spin iron(II) species at room temperature. The crystal and molecular structure of [Fe(5NO2-salaep)2] (1) has been determined. 1 crystallizes in the orthorhombic system, space group Pbcn with Z=4 and a=14.756(3), b=9.682(3), c=18.632(4) Å. The structure was solved by the heavy-atom method and refined to conventional agreement indices R=0.042 and Rw=0.043 with 2845 unique reflections for which I>3σ. The structure of 1 consists of [Fe(5NO2-salaep)2] complex molecules stacked through π interactions involving the salicylaldimine rings of adjacent molecules to afford ribbons along the [001] direction. The central iron atom of each molecule is triply coordinated to two 5NO2-salaep ligands, affording a distorted coordination octahedron. The Mössbauer spectroscopy is consistent with an increase of the distortion of the iron(II) ligand environment in the series from Fe11(5NO2,-salaep)2] (1) to Fe11[5NO2-sal-N(1,5,9,13)] (4). The variable temperature magnetic susceptibility evidences appreciable zero-field splitting of the iron(II) ground state in [Fe11(5NO2-salaep)2] (1) and Fe11[5NO2-sal-N(1,5,8,12)] (3). 1 exhibits several properties required to afford a modelling of the iron center of the ‘ferroquinone complex’ of photosystem 2. Fe11[5NO2-sal-N(1,4,7,10)] (2) exhibits a thermally induced 5T2g ↔ 1A1g spin conversion with unprecedented features: iron(II) center in a N4O2 ligand environment, spin conversion of discontinuous nature occurring in two steps separated by a 30 K broad spin equilibrium domain in which c. 50% of high-spin and low-spin molecules coexist." @default.
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- W2052524378 date "1991-02-01" @default.
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- W2052524378 title "Iron(II) complexes with polydentate Schiff base ligands as models of the photosynthetic mononuclear non-heme ferrous sites. Synthesis, characterization, molecular crystal structure, EXAFS and XANES studies, Mössbauer spectroscopy and magnetic properties" @default.
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- W2052524378 doi "https://doi.org/10.1016/s0020-1693(00)83060-1" @default.
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