First crystal structures of oxo-bridged [CrIIITaV] dinuclear complexes Spectroscopic, magnetic and theoretical investigations of the Cr-O-Ta core

Abstract : Heterodinuclear complexes [Cr(bpy)2(H2O)(μ-O)Ta(C2O4)3]2·3.5H2O (1) and [H2(terpy)][Cr(terpy)(C2O4)(μ-O)Ta(C2O4)3]·0.5H2C2O4·2.5H2O (2) (bpy = 2,2′-bipyridine; terpy = 2,2′6′,2′′-terpyridine) have been synthesised through a reaction of a tris(oxalate)oxotantalate(v) anion and a complex chromium(iii) cation with corresponding aromatic N-donor ligands. These are the first examples of a Cr-O-Ta bridge in molecular compounds, and the first report of heterodinuclear complexes prepared from a tris(oxalate)oxotantalate(v) anion as a building block. Structural analysis of both compounds revealed that TaV in pentagonal bipyramid geometry is connected through a slightly bent μ-O bridge to CrIII having a distorted octahedral environment. The geometry optimization performed with density functional theory (DFT) calculations gave very good agreement with the experimentally obtained structure of 1. Room temperature solid state UV-Vis spectra were recorded for both compounds and compared to those of starting reagents, in order to test for possible new electronic transitions attributed to the metal-to-metal charge transfer between CrIII and TaV through the oxo-bridge. Infrared (IR) spectroscopy supported with DFT calculations was used to assign vibrational modes to all spectral features, especially those coming from the molecular μ-oxo bridge. Temperature dependence of magnetic properties of 1 and 2 were probed with magnetic susceptibility measurements on a SQUID magnetometer. Additionally, zero-field splitting parameters were determined from electron paramagnetic resonance (EPR) spectra of compound 1 and experimentally obtained values were confirmed by DFT calculations. © 2018 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
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L. Androš Dubraja, M. Jurić, W. Lafargue-Dit-Hauret, D. Pajić, A. Zorko, et al.. First crystal structures of oxo-bridged [CrIIITaV] dinuclear complexes Spectroscopic, magnetic and theoretical investigations of the Cr-O-Ta core. New Journal of Chemistry, Royal Society of Chemistry, 2018, 42 (13), pp.10912-10921. ⟨10.1039/c8nj01493k⟩. ⟨hal-01835067⟩

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