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Issue 8, 2016
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Structural, electrochemical and magnetic analyses of a new octanuclear MnIII2MnII6 cluster with linked-defect cubane topology

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Abstract

The employment of the 3,5-dimethyl-1-(hydroxymethyl)-pyrazole (Hdmhmp) ligand in a manganese carboxylate cluster afforded the new mixed-valent octanuclear manganese cluster [MnIII2MnII6O2(PhCOO)10(dmhmp)4(H2O)2]·4CH3CN (1). Complex 1 was isolated by the reaction of Mn(ClO4)2·6H2O, Hdmhmp and benzoic acid in a mixed solvent of acetonitrile and methanol. The structure of 1 can be described as a μ4-O2−-linked pair of [Mn4O3] defect cubanes protected by ten PhCO2 and four μ3-dmhmp ligands. Complex 1 is slightly soluble in acetonitrile, and high-resolution electrospray mass spectrometry (HRESI-MS) indicated that it could keep the [MnIII2MnII6O2] core integrity in solution but with detectable ligand exchange between PhCOO and dmhmp. The electrochemical studies show that 1 possesses a characteristic MnII → MnIII oxidation peak at +0.82 V and MnIII → MnII reduction peaks at −0.79 and −1.51 V (versus Fc/Fc+), respectively. A detailed magnetic properties investigation has revealed only a weak intramolecular antiferromagnetic interaction between the MnII and MnIII ions and no characteristic single-molecule magnetic properties.

Graphical abstract: Structural, electrochemical and magnetic analyses of a new octanuclear MnIII2MnII6 cluster with linked-defect cubane topology

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Supplementary files

Article information


Submitted
12 Nov 2015
Accepted
22 Jan 2016
First published
25 Jan 2016

CrystEngComm, 2016,18, 1329-1336
Article type
Paper
Author version available

Structural, electrochemical and magnetic analyses of a new octanuclear MnIII2MnII6 cluster with linked-defect cubane topology

F. Yang, Y. Deng, L. Guo, H. Su, Z. Jagličić, Z. Feng, G. Zhuang, S. Zeng and D. Sun, CrystEngComm, 2016, 18, 1329
DOI: 10.1039/C5CE02215K

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