Publication in RSC Advances

The objective of this work was the exploration of the effect of the second coordination sphere on the magnetic properties of [Ln(NO3)3(H2O)3]·(18C6) (Ln = Dy (1), Er (2)) compounds comprising cocrystallized 18-crown-6 ethers. Both compounds were identified as field-induced single molecule magnets (SMMs) with estimated magnetization reversal barriers Ueff = 66–71 K for 1 and Ueff = 21–24 K for 2. Theoretical calculations with the B3LYP functional revealed substantial change and redistribution of the electrostatic potential upon accounting for the second coordination sphere represented by two 18C6 molecules, which resulted in the change of the crystal-field around metal atoms. As a result, the multireference CASSCF calculations exposed significant impact of the second coordination sphere on the energy splitting of the respective 6H15/2 DyIII and 4I15/2 ErIII ground states, the magnetization reversal barrier and the magnetic anisotropy parameters. Moreover, the calculated magnetization reversal barriers, Ucalc. = 57 K for 1 and Ucalc. = 16 K for 2, are in good agreement with the experimental values accentuating the importance of the second coordination sphere on the magnetic properties of SMMs.


Date: 16. jan 2019 | Author: agch

Department of Inorganic Chemistry

Faculty of Science
Palacký University in Olomouc

17. listopadu 12
CZ-771 46 Olomouc
Czech Republic

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email : agch(at)