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A mixed-valence metallogrid [CoCo] with an unusual electronic structure and single-ion-magnet characterization
Wei Huang1, Feifei Pan, Zhenxing Wang
1Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Collaborative Innovation Center of Advanced Catalysis & Green Manufacturing, School of Petrochemical Engineering, Changzhou University, Changzhou, Jiangsu 213164, China. wudy@cczu.edu.cn fengxuejun@cczu.edu.cn.
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-[Co-Co-Co-Co]. 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.