Disk-like Hepta- and Tridecanuclear Cobalt Clusters. Synthesis, Structure, Magnetic Properties and DFT calculations

Ji-Dong Leng; Su-Kun Xing; Radovan Herchel; Ming-Liang Tong

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Disk-like Hepta- and Tridecanuclear Cobalt Clusters. Synthesis, Structure, Magnetic Properties and DFT calculations

Ji-Dong Leng 1,Su-Kun Xing 1,Radovan Herchel 2,Ming-Liang Tong 1 * #

1.School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275

2.Department of Inorganic Chemistry, Palacky University

*Correspondence author

#Submitted by

Subject:

Funding: SRFDP（No.20100171110015）, NSFC（No.91122032, 21201182 and 21121061）, Operational Program Research and Development for Innovations Ministry of Education, Youth and Sports of the Czech Republic（No.CZ.1.05/2.1.00/03.0058）, “973 Project”（No.2012CB821704, 2014CB845602）

Opened online: 7 January 2014

Accepted by: none

Citation: Ji-Dong Leng,Su-Kun Xing,Radovan Herchel.Disk-like Hepta- and Tridecanuclear Cobalt Clusters. Synthesis, Structure, Magnetic Properties and DFT calculations[OL]. [ 7 January 2014] http://en.paper.edu.cn/en_releasepaper/content/4578447

The synthesis, structure and magnetic properties are reported of two disk-like mixed-valence cobalt clusters [CoIIICoII6(thmp)2(acac)6(ada)3] (1) and [CoIII2CoII11(thmp)4(Me3CCOO)4(acac)6(OH)4(H2O)4](Me3CCOO)2.H2O (2). Heptanuclear complex 1 was prepared by solvothermal reaction of cobalt(II) acetylacetonate (Co(acac)2), 1,1,1-tris(hydroxymethyl)-propane (H3thmp), and adamantane-1-carboxylic acid (Hada), whereas by substituting Hada with (CH3)3CCO2H, tridecanuclear complex 2 was obtained with an unexpected [CoIII2CoII11] core. The core structures of 1 and 2 are related to each other: that of 1 arrange as a centered hexagon of a central CoIII ion surrounded by a [CoII6] hexagon, while that of 2 can be described as a larger oligomer based on two vertex sharing [CoIIICoII6]. Variable-temperature direct current (dc) magnetic susceptibility measurements demonstrated overall ferromagnetic coupling between the CoII ions within both two clusters. The magnetic exchange (J) and magnetic anisotropy (D) was quantified with appropriate spin Hamiltonians models and also supported by DFT calculations. The presence of frequency-dependent out-of-phase ac susceptibility signals at temperatures below 3 K suggested that 2 might be a single-molecule magnet.

Keywords:cobalt cluster; structure; magnetic properties; DFT studies

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