Abstract
A new tetranuclear mixed-valence manganese(II/IV) compound [MnIIMnIV3(μ-Cl)3(µ3-O)(L)3] (1) (where H3L = (3E)-3-((Z)-4-hydroxy-4-phenylbut-3-en-2-ylideneamino)propane-1,2-diol) has been synthesized and characterized by different physicochemical methods. Single crystal X-ray diffraction analysis reveals that 1 is a tetrahedral cluster consisting of a Mn4Cl3O4 core in which the only Mn(II) ion is joined through three μ2-O bridges to an equilateral triangle of Mn(IV) ions, which are connected by a μ3-O and three μ2-Cl bridges. The redox behavior of 1 was studied by cyclic voltammetry. Variable temperature magnetic susceptibility measurements of 1 revealed predominant antiferromagnetic coupling inside the Mn4Cl3O4 cluster.
Highlights
Paramagnetic metal clusters are widely utilized in magnetic, electronic, optical, biological, and catalytic studies and applications [1,2]
Schiff bases derived from amino alcohols have proven to possess the ability to form polynuclear complexes [1,2], which play a significant role as biomimetic models of metallobiomolecules [8,9]
Mn(IV)–Cl distances in the range 2.663(3)–2.719(3) Å observed in 1 are slightly higher in comparison to the Mn(III)–Cl distances found in the range 2.631(5)–2.712(3) Å for the reported mixed valence manganese complex (YEMBOK) [1] with a MnIIMnIII3(μ-Cl)3(μ3-O) triangular planar core
Summary
Paramagnetic metal clusters are widely utilized in magnetic, electronic, optical, biological, and catalytic studies and applications [1,2]. Catalytic and magnetic behaviors of many mixed-valence manganese complexes have been investigated using different synthetic strategies [4,10]. The most common oxidation state originates in these hetero-valence manganese complexes are MnII, MnIII and MnIV [11,12,13]. Due to the presence of numerous possibilities in different magnetic coupling between pairs of ions in various oxidation states (II/II, II/III, II/IV, III/III, III/IV and IV/IV pairs), very high values of total molecular spin (S) [14,15,16,17] are an expected phenomenon in these complexes. Schematic diagram for the synthesis of the Schiff base (H3L) and its deprotonated form (L3−). Scheme 1.Schematic diagram for the synthesis of the Schiff base (H3L) and its deprotonated form (L3−)
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