The odd association of a C3h trisamidinium cation and tosylate anion with a series of linear oxalate-bridged trinuclear heterometallic complexes - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Dalton Transactions Année : 2013

The odd association of a C3h trisamidinium cation and tosylate anion with a series of linear oxalate-bridged trinuclear heterometallic complexes

Résumé

A series of six isostructural heterometallic trinuclear oxalate-bridged complexes of formula (TDbenz)2(TsO)2[M II (H2O)2{(µ-ox)M III (ox)2}2]. 6H2O. 2CH3OH (TDbenz = 1,3,5-tris[2-(1,3diazolinium)]benzene; TsO = 4-methylbenzenesulfonate; ox = oxalate; M III = Fe, M II = Mn (1), Fe (2), Co (3); M III = Cr, M II = Mn (4), Fe (5), Co (6)) have been synthesized from (NH4)3[M III (ox)3]. 3H2O, the chloride salts of the divalent metal ions and the tosylate salt of 1,3,5-tris[2-(1,3-diazolinium)]benzene (trisamidinium). Whereas the crystal structures of compounds 2, 3, 4 and 5 have been investigated by single-crystal X-ray diffraction, the structures of 1 and 6 have been checked by X-ray powder diffraction. All six compounds are isostructural and crystallise in the Pī space group. The crystals are composed of discrete linear [M II (H2O)2{(µ-ox)M III (ox)2}2] 4trinuclear bimetallic units, trisamidinium and tosylate ions and solvent molecules. The linear trinuclear unit is based on a central trans-diaquametal(II) entity connected to two [M III (ox)3] 3-(M III = Cr III , Fe III) moieties through oxalate bridges. The divalent metal ions, surrounded by six oxygen atoms, adopt a distorted octahedral coordination geometry. The coordination sphere is composed of four oxygen atoms belonging to two oxalate ligands and two transcoordinated water molecules. One of the oxalate ions is coordinated to the central metal centre whereas the other two oxalate ligands are non-bridging. In the crystal, intermolecular hydrogen bonds involving oxalate ligands, solvent molecules and the counter-ions form a complex 3D network. Variabletemperature magnetic susceptibility measurements indicate an antiferromagnetic interaction between the iron(III) and the metal(II) ions (J =-4.23,-6.73,-8.97 cm-1 for 1, 2 and 3 respectively) whereas this interaction is ferromagnetic when iron(III) is replaced by chromium(III) (J = +1.21, +2.20, +3.63 cm-1 for 4, 5 and 6 respectively). Moreover, the cobalt(II) derivatives exhibit high D values (D = 29.3 cm-1 for 3 and D = 27.4 cm-1 for 6).
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hal-01991213 , version 1 (24-11-2020)

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Catalin Maxim, Emilio Pardo, Mir Wais Hosseini, Sylvie Ferlay, Cyrille Train. The odd association of a C3h trisamidinium cation and tosylate anion with a series of linear oxalate-bridged trinuclear heterometallic complexes. Dalton Transactions, 2013, 42 (13), pp.4704. ⟨10.1039/C3DT32770A⟩. ⟨hal-01991213⟩
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