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Mixed-Valent Trinuclear CoIII-CoII-CoIII Complex with 1,3-Bis(5-chlorosalicylideneamino)-2-propanol

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A mixed-valent trinuclear complex with 1,3-bis(5-chlorosalicylideneamino)-2-propanol (H3clsalpr) was synthesized, and the crystal structure was determined by the single-crystal X-ray diffraction method at 90 K. The molecule is a trinuclear CoIII-CoII-CoIII… Click to show full abstract

A mixed-valent trinuclear complex with 1,3-bis(5-chlorosalicylideneamino)-2-propanol (H3clsalpr) was synthesized, and the crystal structure was determined by the single-crystal X-ray diffraction method at 90 K. The molecule is a trinuclear CoIII-CoII-CoIII complex with octahedral geometries, having a tetradentate chelate of the Schiff-base ligand, bridging acetate, monodentate acetate coordination to each terminal Co3+ ion and four bridging phenoxido-oxygen of two Schiff-base ligands, and two bridging acetate-oxygen atoms for the central Co2+ ion. The electronic spectral feature is consistent with the mixed valent CoIII-CoII-CoIII. Variable-temperature magnetic susceptibility data could be analyzed by consideration of the axial distortion of the central Co2+ ion with the parameters Δ = –254 cm−1, λ = –58 cm−1, κ = 0.93, tip = 0.00436 cm3 mol−1, θ = –0.469 K, gz = 6.90, and gx = 2.64, in accordance with a large anisotropy. The cyclic voltammogram showed an irreversible reduction wave at approximately −1.2 V·vs. Fc/Fc+, assignable to the reduction of the terminal Co3+ ions.

Keywords: coiii; mixed valent; valent trinuclear; coii coiii; coiii coii

Journal Title: Molecules
Year Published: 2022

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