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Issue 15, 2017
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A mixed-valence metallogrid [CoIII2CoII2] with an unusual electronic structure and single-ion-magnet characterization

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Abstract

The reaction of the multisite coordination ligand (H2L) with Co(Ac)2·4H2O in the absence of any base affords a homometallic tetranuclear mixed-valence complex, [Co4(L)4(CH3CO2)2(CH3OH)2]·Et2O (1). This mixed-valence metallogrid [Co4(L)4(CH3CO2)2 (CH3OH)2]·Et2O (1) has been theoretically and experimentally analyzed to assign the valence and spin state in the form of trans-[CoIIIls–CoIIhs–CoIIIls–CoIIhs]. HF-EPR reveals the presence of axial anisotropy (D = −34.4 cm−1) with a significant transverse component (E = 9.5 cm−1) in the local high spin cobalt centers. Slow magnetic relaxation effects were observed in the presence of a dc field, demonstrating field-induced single ion magnetic behavior, which is associated with the unusual electronic structure of Co(II) within the metallogrid.

Graphical abstract: A mixed-valence metallogrid [CoIII2CoII2] with an unusual electronic structure and single-ion-magnet characterization

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Publication details

The article was received on 15 Feb 2017, accepted on 17 Mar 2017 and first published on 17 Mar 2017


Article type: Paper
DOI: 10.1039/C7DT00564D
Citation: Dalton Trans., 2017,46, 5069-5075
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    A mixed-valence metallogrid [CoIII2CoII2] with an unusual electronic structure and single-ion-magnet characterization

    W. Huang, F. Pan, Z. Wang, Y. Bai, X. Feng, J. Gu, Z. Ouyang and D. Wu, Dalton Trans., 2017, 46, 5069
    DOI: 10.1039/C7DT00564D

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