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Field-induced slow relaxation of magnetization in dinuclear and trinuclear CoIII?MnIII complexes

机译：DiaNI-Ex诱导的二维和三核COIII中磁化缓慢放松？MNIII复合物

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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)} _(2) Mn(L4a)]I ( 3 ) and [{Co(3EtO-L5)(μ-CN)} _(2) Mn(L4a)](NO _(3) ) ( 4 ) complexes were prepared and thoroughly characterized (H _(2) 3EtO-L5 = N , N ′-bis(3-ethoxy-2-hydroxybenzylidene)-1,6-diamino-3-azahexane, L4a ~(2?) = 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: D _(calc) ( E _(calc) / D _(calc) ) = ?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 ( U _(eff) ) and relaxation time ( τ _(0) ) was used, and the values of U _(eff) ranging from 11 to 20 K and t _(0) from 0.1 to 19 × 10 ~(?7) s were obtained.
机译：两种新的二核，[CO（3×15）（μ-CN）Mn（L4a）Cl]（1）和[Co（3×L5）（μ-CN）Mn（L4a）Br]（2），以及两个三核[{CO（3etO-L5）（μ-CN）} _（2）Mn（L4a）] I（3）和[{Co（3etO-L5）（μ-CN）} _（2）Mn（L4a ）]（没有制备和彻底地表征（4）络合物（H _（2）3×15 = N，N'（3-乙氧基-2-羟基苄基）-1,6-二氨基 - 3-己烷，L4A〜（2？）= N，N' - 乙烷 - 双（水杨酸酯）Dianion）。确定所有四种化合物的晶体结构，而仅对化合物1-3进行静态和动态磁性。通过同时拟合温度和场依赖性磁数据，并通过使用涉及轴向各向异性术语的旋转哈密顿的形式主义来揭示载锰（III）原子在1-3中具有相对大的阴性轴向磁各向异性，D =？ 3.9（2）cm〜（？1）在1，α4.9（2）cm〜（α1）2中，α4.1（1）cm〜（？1）3。这些结果由AB初始Casscf计算支持，与实验结果吻合良好，但计算了与实验评估相反的小菱形：D _（Calc）（E _（Calc）/ D _（Calc）） =？3.2cm〜（α1）（0.04）在1中，2℃，2.30cm〜（0.03），3.6cm〜（0.04）3。动态磁数据的测量证实，化合物1-3代表了一种新型的MN（III）场诱导的单离子磁体。频率依赖性超相敏感性的峰值最大值低于所有三种情况下的最低可接触温度（即1.9 k），这阻止了我们的结构图。然而，使用旋转反转屏障（U _（EFF））和弛豫时间（τ_（0））的近似过程，以及从11到20 k和t _的u _（eff）的值。 （0）获得0.1至19×10〜（？7）S。

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