A trapped hexaaqua CoII complex between the polyanionic sheets of decavanadate reveals high axial anisotropy and field induced SIM behaviour
- 21 March 2021
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Dalton Transactions
- Vol. 50 (11), 3825-3831
- https://doi.org/10.1039/d0dt04339g
Abstract
In this work, we report an inorganic compound [{Co(H2O)(6)}(2+){Na4V10O28}(2-)] (1) in which the polyanionic sheets of decavanadate play the role of a diamagnetic matrix that reduces the dipolar-dipolar and spin-spin interactions between [Co(H2O)(6)](+2) units to suppress the fast tunnelling of magnetization. Structural analysis reveals that each [Co(H2O)(6)](+2) complex is surrounded by four decavanadates and separated by a large internuclear distance (9 angstrom). It was also found that the adjacent decavanadates are connected via sodium ions and form a 2D sheet of the inorganic layer in which the [Co(H2O)(6)](2+) ions are present in between two layers. Detailed dc (direct current) and ac (alternating current) magnetic measurements disclose the presence of large easy-axis anisotropy (D = -102 cm(-1)) and field induced slow magnetic relaxation behaviour with a spin reversal barrier of U-eff = 50 K. Additionally, the temperature dependence of the relaxation time reveals that the Raman and QTM processes mainly play an important role rather than the thermally activated Orbach process in the overall relaxation dynamics of the studied compound. To analyse the electronic structure and magnetic properties of compound 1, ab initio calculations were performed which further support the experimental observations. Notably, the U-eff value of 1 represents the highest energy barrier reported for POM based SMMs with transition metal ions to date.Funding Information
- University Grants Commission
- Science and Engineering Research Board (CRG/2018/000072)
- Council of Scientific and Industrial Research, India (01(2974)/19/EMR-II)
- Indian Institute of Science Education and Research Bhopal
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