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Issue 26, 2013
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Structural and magnetic characterizations of the first manganese(III) Schiff base complexes involving hexathiocyanidoplatinate(IV) bridges

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Abstract

The reactions of [MnIII(L4a)Cl] or [MnIII(L4b)Cl] with [Pt(SCN)6]2− resulted in the formation of a 1D polymeric complex [{Mn(L4a)}2{μ-Pt(SCN)6}]n (1) and a trinuclear compound [{Mn(L4b)(H2O)}2{μ-Pt(SCN)6}] (2), where L4a and L4b are tetradentate dianionic Schiff base ligands, H2L4a = N,N′-ethylenebis(salicylimine) and H2L4b = N,N′-3-methylbenzenebis(3-ethoxysalicylimine). In compound 1, the adjacent [Mn(L4a)]+ subunits are bound together through the phenolic oxygen atoms, thus forming [{Mn(L4a)}2]2+ dimers with the shortest Mn⋯Mn distance of 3.2101(5) Å, while in compound 2, the intermolecular bifurcated O–H⋯O hydrogen bonds between the neighbouring molecules form [{Mn(L4b)(H2O)}2]2+ dimers, resulting in a supramolecular 1D chain structure. The Mn⋯Mn distance within the supramolecular dimer is 4.7007(9) Å, while the shortest Mn⋯Mn distance between the dimers is 9.2347(10) Å. The magnetic analyses comprising the zero-field splitting resulted in a ferromagnetic exchange interaction within the phenolato-bridged dimer in 1 (J = +1.73 cm−1, DMn = −2.65 cm−1) and the antiferromagnetic exchange interaction within the supramolecular dimer in 2 (J = −0.88 cm−1, DMn = −3.06 cm−1). The experimental findings regarding the dominant as well as negligible exchange pathways are in good agreement with the results from DFT calculations at the B3LYP/TZVP level of theory.

Graphical abstract: Structural and magnetic characterizations of the first manganese(iii) Schiff base complexes involving hexathiocyanidoplatinate(iv) bridges

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Publication details

The article was received on 25 Mar 2013, accepted on 30 Apr 2013 and first published on 01 May 2013


Article type: Paper
DOI: 10.1039/C3CE40524A
Citation: CrystEngComm, 2013,15, 5351-5358
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    Structural and magnetic characterizations of the first manganese(III) Schiff base complexes involving hexathiocyanidoplatinate(IV) bridges

    T. Šilha, I. Nemec, R. Herchel and Z. Trávníček, CrystEngComm, 2013, 15, 5351
    DOI: 10.1039/C3CE40524A

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