[LnIII-MnII-LnIII] heterometallic compounds: rare linear SMMs with divalent manganese ions
[LnIII-MnII-LnIII] heterometallic compounds: rare linear SMMs with divalent manganese ions
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[Ln(III)-Mn-II-Ln(III)]异金属化合物：稀有的具有二价锰离子的线性SMM
DOI：
10.1039/c4dt03713h
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发表时间：
2015-01-01
影响因子：
4
通讯作者：
Tang, Jinkui
中科院分区：
文献类型：
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作者：
Li, Xiao-Lei;Min, Fan-Yong;Tang, Jinkui
Mn（OAc）（2）中心点4 H（2）O和Ln（NO3）（3）中心点6 H（2）O与N-（2-氨丙基）-2-羟基苯甲酰胺和水杨醛在甲醇/二氯甲烷中反应，在三乙胺存在下生成黄色晶体Ln（2）Mn（C7 H5 O2）（8）（Ln = Gd（1），Tb（2），Dy（3），Ho（4）和Er（5））。三个金属离子通过六个水杨醛配体的六个μ（2）-酚氧连接，得到了理想的线性[Ln（III）-Mn-II-Ln（III）]结构。这些复合物的磁性研究已经进行和交流磁化率测量显示存在的温度依赖性的相位的交流信号的复合物2和3指示单分子磁体（SMM）的行为。（Dy 2 MnII）-Mn-III化合物显示出双弛豫途径，这可能分别源于单个Dy-III离子的单离子行为和Dy-III与Mn-II离子之间的弱耦合。92.4（2）K的U-eff是3d-4f SMM中相对较高的值。此外，配合物2和3代表了我们所知的第一个只含二价锰离子的线性Mn-Ln自组装金属材料。结果表明，磁耦合的积极影响，以提高他们的SMM行为，提出了一个有前途的策略，构建高效的异质结SMM。
The reaction of Mn(OAc)(2)center dot 4H(2)O and Ln(NO3)(3)center dot 6H(2)O with N-(2-aminopropyl)-2-hydroxybenzamide and salicylic aldehyde in methanol/methylene dichloride produces yellow crystals of Ln(2)Mn(C7H5O2)(8) (Ln = Gd (1), Tb (2), Dy (3), Ho (4) and Er (5)), in the presence of triethylamine. Three metal ions are connected by six mu(2)-phenolate oxygen atoms of six salicylic aldehyde ligands, resulting in perfect linear [Ln(III)-Mn-II-Ln(III)] structures. Magnetic studies of these complexes have been performed and AC susceptibility measurements show the presence of a temperature-dependent out-of-phase ac signal for complexes 2 and 3 indicating single-molecule magnet (SMM) behavior. The (Dy2MnII)-Mn-III compound shows double relaxation pathways which may originate from the single ion behavior of individual Dy-III ions and the weak coupling between Dy-III and Mn-II ions, respectively. The U-eff of 92.4(2) K is a relatively high value among 3d-4f SMMs. Moreover, complexes 2 and 3 represent the first linear Mn-Ln SMMs containing only divalent manganese ions as far as we know. The result suggests the positive effects of magnetic coupling to enhance their SMM behavior, presenting a promising strategy for constructing efficient heterometallic SMMs.