A Dysprosium Metallocene Single-Molecule Magnet Functioning at the Axial Limit
A Dysprosium Metallocene Single-Molecule Magnet Functioning at the Axial Limit
复制标题
轴向极限作用的镝茂金属单分子磁体
DOI：
10.1002/ange.201705426
复制
发表时间：
2017
影响因子：
--
通讯作者：
Guo F
中科院分区：
文献类型：
--
作者：
Guo F
通过三乙基甲硅烷基阳离子从金属镝[（Cpttt）2DyCl]（1DyCpttt= 1，2，4-三（叔丁基）环戊二烯）中提取氯化物配体产生第一种无碱稀土金属镝阳离子[（Cpttt）2Dy]+（2Dy），作为非配位[B（C6 F5）4]−阴离子的盐。磁性测量表明，[2Dy][B（C6 F5）4]是一种SMM，在零磁场下具有高达1277cm−1（1837 K）的各向异性势垒和60 K的记录磁阻塞温度，包括磁滞和矫顽力。 计算研究进一步强调了2Dy的特殊磁轴性，这表明该系统是第一个镧系SMM，其中所有低位Kramers双峰对应于一个明确的MJ值，即使在较高的双峰中也没有明显的混合。
Abstraction of a chloride ligand from the dysprosium metallocene [(Cpttt)2DyCl] (1DyCpttt=1,2,4‐tri(tert‐butyl)cyclopentadienide) by the triethylsilylium cation produces the first base‐free rare‐earth metallocenium cation [(Cpttt)2Dy]+(2Dy) as a salt of the non‐coordinating [B(C6F5)4]−anion. Magnetic measurements reveal that [2Dy][B(C6F5)4] is an SMM with a record anisotropy barrier up to 1277 cm−1(1837 K) in zero field and a record magnetic blocking temperature of 60 K, including hysteresis with coercivity. The exceptional magnetic axiality of2Dyis further highlighted by computational studies, which reveal this system to be the first lanthanide SMM in which all low‐lying Kramers doublets correspond to a well‐definedMJvalue, with no significant mixing even in the higher doublets.