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Self-assembly, structures, magnetic properties and solution behaviors of six mixed-valence cobalt clusters

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Abstract

The introduction of multidentate chelating ligands and secondary small inorganic anions into a variable-valence cobalt synthesis system led to the formation of six novel mixed-valence cobalt clusters, namely, [CoII2CoIII2(mdea)2(OH)2(2,2′-bipy)2(CH3CN)4]·4ClO4·2H2O (SD/Co1), [CoII2CoIII2(dmhmp)6(CH3CN)4]·4ClO4·4CH3CN (SD/Co2), [CoIICoIII4(mdea)4(N3)4(piv)2] (SD/Co3), [CoII2CoIII2Na(mdea)2(N3)(piv)8] (SD/Co4), [CoII4CoIII2(dea)2(Hdea)4(piv)4]·2piv (SD/Co5), and [CoII2CoIII2(mdea)2(dmpea)2(OH)2(CH3CN)2(H2O)2]·4ClO4·2H2O (SD/Co6) (H2dea = diethanolamine, H2mdea = N-methyldiethanolamine, 2,2′-bipy = 2,2′-bipyridine, Hdmhmp = 3,5-dimethyl-1-(hydroxymethyl)-pyrazole, Hpiv = pivalic acid and dmpea = 1-(3,5-dimethyl-1H-pyrazol-1-yl)-ethanimine). Among them, compounds SD/Co1, SD/Co2 and SD/Co6 have a similar cationic tetranuclear core motif {Co4O6} consisting of two CoIII and two CoII mixed-valence ions. Compound SD/Co3 has two similar neutral pentanuclear {Co5O8} clusters co-crystallized in one asymmetric unit that each contains four CoIII ions and one CoII ion. Compound SD/Co4 consists of a bimetallic pentanuclear calyx-like {Co4Na} skeleton including two CoIII and two CoII ions, while compound SD/Co5 has a cationic hexanuclear rod-like cluster {Co6O8} consisting of two CoIII and four CoII ions. In addition, the high-resolution electrospray ionization mass spectrometry (HRESI-MS) technique was introduced to detect their solution behaviors and reveal their evolutional processes. Magnetic measurements indicated that these cobalt clusters show distinct magnetic behaviors at low temperature.

Graphical abstract: Self-assembly, structures, magnetic properties and solution behaviors of six mixed-valence cobalt clusters

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Publication details

The article was received on 26 Jul 2017, accepted on 04 Sep 2017 and first published on 04 Sep 2017


Article type: Paper
DOI: 10.1039/C7CE01375B
Citation: CrystEngComm, 2017, Advance Article
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    Self-assembly, structures, magnetic properties and solution behaviors of six mixed-valence cobalt clusters

    Y. Li, L. Guo, L. Feng, Z. Jagličić, S. Zeng and D. Sun, CrystEngComm, 2017, Advance Article , DOI: 10.1039/C7CE01375B

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