A High-Performance Single-Molecule Magnet Utilizing Dianionic Aminoborolide Ligands
A High-Performance Single-Molecule Magnet Utilizing Dianionic Aminoborolide Ligands
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DOI：
10.1021/jacs.2c06698
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发表时间：
2022-09-26
影响因子：
15
通讯作者：
Nippe, Michael
中科院分区：
文献类型：
--
作者：
Vanjak, James C.;Wilkins, Branford O.;Nippe, Michael
提出了均配f-块硼氢化物夹心复合物的第一个例子，并示出其是高性能的单分子磁体（SMM）。国际清算银行（硼）配合物[K（2.2.2）][[1-（哌啶子基）-2，3，4，5-四苯基硼杂环戊烯基]2Dy]（1）的特征在于阴离子Ln 3+茂金属的不寻常实例，其支持短金属-配体键和围绕中心Dy 3+离子的高度线性，导致相对大的磁化反转势垒（对于最线性的取向，Ueff = 1600 cm-1），并且重要的是，66 K的高阻断温度（TB，定义为T（r100 s））。这些指标将复合物1置于迄今为止报道的表现最好的SMM中，并突出了与单阴离子环状配体相比，双阴离子硼氢化物配体增加配体场轴性的潜力，以最终使基于f-嵌段的SMM中的磁各向异性最大化。
The first example of a homoleptic f-block borolide sandwich complex is presented and shown to be a highperformance single-molecule magnet (SMM). The bis(borolide) complex [K(2.2.2)][[1-(piperidino)-2,3,4,5-tetraphenylborolyl]2Dy] (1) features an unusual example of an anionic Ln3+ metallocene that supports short metal-ligand bonds and a high degree of linearity around the central Dy3+ ion, resulting in comparatively large barriers to magnetization reversal (Ueff = 1600 cm-1 for the most linear orientation) and, importantly, a high blocking temperature (TB, defined as T(r100s)) of 66 K. These metrics put complex 1 among the very best performing SMMs reported to date and highlight the potential of dianionic borolide ligands to increase ligand field axiality, compared to monoanionic cyclic ligands, to ultimately maximize magnetic anisotropy in f-block-based SMMs.