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Issue 4, 2016
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Field-induced slow relaxation of magnetization in dinuclear and trinuclear CoIII⋯MnIII complexes

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Abstract

Two new dinuclear, [Co(3EtO-L5)(μ-CN)Mn(L4a)Cl] (1) and [Co(3EtO-L5)(μ-CN)Mn(L4a)Br] (2), and two trinuclear [{Co(3EtO-L5)(μ-CN)}2Mn(L4a)]I (3) and [{Co(3EtO-L5)(μ-CN)}2Mn(L4a)](NO3) (4) complexes were prepared and thoroughly characterized (H23EtO-L5 = N,N′-bis(3-ethoxy-2-hydroxybenzylidene)-1,6-diamino-3-azahexane, L4a2− = N,N′-ethane-bis(salicylideneiminate)dianion). The crystal structures were determined for all four compounds, while the static and dynamic magnetic properties were studied only for compounds 1–3. It has been revealed by simultaneous fitting of temperature and field dependent magnetic data and by using the spin Hamiltonian formalism involving the axial anisotropy term that the manganese(III) atoms possess relatively large and negative axial magnetic anisotropy in 1–3, with D = −3.9(2) cm−1 in 1, −4.9(2) cm−1 in 2, and −4.1(1) cm−1 in 3. These results were supported by ab initio CASSCF calculations which were in good agreement with the experimental ones, however, a small rhombicity was calculated contrary to the experimental evaluations: Dcalc(Ecalc/Dcalc) = −3.2 cm−1 (0.04) in 1, −3.0 cm−1 (0.03) in 2, and −3.6 cm−1 (0.04) in 3. The measurements of dynamic magnetic data confirmed that compounds 1–3 represent a new type of Mn(III) field-induced single-ion magnet. The peak maxima of the frequency dependent out-phase susceptibility were below the lowest accessible temperature in all the three cases (i.e. below 1.9 K) and this prevented us from the construction of the Argand diagram. Nevertheless, the approximate procedure for extracting the spin-reversal barrier (Ueff) and relaxation time (τ0) was used, and the values of Ueff ranging from 11 to 20 K and t0 from 0.1 to 19 × 10−7 s were obtained.

Graphical abstract: Field-induced slow relaxation of magnetization in dinuclear and trinuclear CoIII⋯MnIII complexes

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Publication details

The article was received on 12 Nov 2015, accepted on 18 Dec 2015 and first published on 22 Dec 2015


Article type: Paper
DOI: 10.1039/C5RA23922B
Citation: RSC Adv., 2016,6, 3074-3083
  • Open access: Creative Commons BY-NC license
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    Field-induced slow relaxation of magnetization in dinuclear and trinuclear CoIII⋯MnIII complexes

    I. Nemec, R. Herchel, Z. Trávníček and T. Šilha, RSC Adv., 2016, 6, 3074
    DOI: 10.1039/C5RA23922B

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