Modulating Single-Molecule Magnetic Behavior of a Dinuclear Erbium(III) Complex by Solvent Exchange.
Jing-Yuan GeLong CuiJing LiFei YuYou SongYi-Quan ZhangJing-Lin ZuoMohamedally KurmooPublished in: Inorganic chemistry (2016)
[Er2(thd)4Pc]·2C6H6 (1) (Hthd = 2,2,6,6-tetramethylheptanedione), obtained as green crystals from the reaction of [Er(thd)3]·2H2O with lithium phthalocyanine, Li2Pc, is a stable dinuclear complex with two ErIII centers. Its lattice benzene solvent can be exchanged by soaking the crystals in dichloromethane to give [Er2(thd)4Pc]·2CH2Cl2 (2). The magnetic susceptibility data suggest different coupling interactions for the two complexes. While 1 exhibits fast relaxation and an estimated energy barrier of Ea = 2.6 cm-1 under 600 Oe dc field, the single-molecule magnet behavior of 2 is field-induced and the energy barrier is higher at 34.3 cm-1. Ab initio calculations were performed to understand the nature of the coupling interaction between two ErIII ions bridged by the phthalocyanine and the origin of different magnetic behavior. Importantly, the single-molecule magnetic properties can be reversibly tuned through the exchange of solvent molecules, confirmed by further measurements on the reverse solvated complexes 1-re and 2-re. This subtle control of relaxation by lattice solvents is rarely observed in single-molecule magnets, especially for ErIII-based complexes.
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