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Issue 34, 2016
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Competitive coordination aggregation for V-shaped [Co3] and disc-like [Co7] complexes: synthesis, magnetic properties and catechol oxidase activity

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Abstract

Unique dependence on the nature of metal salt and reaction conditions for coordination assembly reactions of varying architecture and nuclearity have been identified in V-shaped [Co3L4] and planar disc-like [Co7L6] compounds: [CoII3L2(μ-L)2(μ-OH2)2(CF3CO2)2] (1) and [CoII7(μ-L)6(μ-OMe)6]Cl2 (2) (HL = 2-{(3-ethoxypropylimino)methyl}-6-methoxyphenol). At room temperature varying reaction conditions, cobalt-ligand ratios and use of different bases allowed unique types of coordination self-assembly. The synthetic marvel lies in the nature of aggregation with respect to the two unrelated cores in 1 and 2. Complex 1 assumes a V-shaped arrangement bound to L, water and a trifluoroacetate anion, while 2 grows around a central CoII ion surrounded by a {CoII6} hexagon bound to methoxide and L. Magnetic measurements revealed that the intermetallic interactions are antiferromagnetic in nature in the case of complex 1 and ferromagnetic in the case of 2 involving high spin cobalt(II) ions with stabilization of the high-spin ground state in the latter case. In MeCN solutions complexes 1 and 2 showed catalytic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBCH2) to 3,5-di-tert-butylbenzoquinone (3,5-DTBQ) in air. The kinetic study in MeCN revealed that with respect to the catalytic turnover number (kcat) 2 is more effective than 1 for oxidation of 3,5-DTBCH2.

Graphical abstract: Competitive coordination aggregation for V-shaped [Co3] and disc-like [Co7] complexes: synthesis, magnetic properties and catechol oxidase activity

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Publication details

The article was received on 21 Jun 2016, accepted on 01 Aug 2016 and first published on 01 Aug 2016


Article type: Paper
DOI: 10.1039/C6DT02494G
Citation: Dalton Trans., 2016,45, 13576-13589
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    Competitive coordination aggregation for V-shaped [Co3] and disc-like [Co7] complexes: synthesis, magnetic properties and catechol oxidase activity

    T. Singha Mahapatra, D. Basak, S. Chand, J. Lengyel, M. Shatruk, V. Bertolasi and D. Ray, Dalton Trans., 2016, 45, 13576
    DOI: 10.1039/C6DT02494G

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