Insight into D 6 h Symmetry: Targeting Strong Axiality in Stable Dysprosium(III) Hexagonal Bipyramidal Single-Ion Magnets
Insight into D 6 h Symmetry: Targeting Strong Axiality in Stable Dysprosium(III) Hexagonal Bipyramidal Single-Ion Magnets
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深入了解 D 6 h 对称性：以稳定镝 (III) 六角双锥单离子磁体中的强轴性为目标
DOI：
10.1002/ange.201907686
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发表时间：
2019
影响因子：
--
通讯作者：
Canaj A
中科院分区：
文献类型：
--
作者：
Canaj A
遵循一种新的合成策略，其中由Ph 3SiO −产生的强单轴配体场（Ph 3SiO −=三苯基硅烷醇的阴离子）和2，4-二-tBu-PhO−（2，4-二叔丁基苯酚的阴离子）配体与配体LN 6的弱赤道场结合，导致[DyIII（LN 6）]（2，4-di-tBu-PhO）2]（PF 6）（1）、[DyIII（LN 6）（Ph 3SiO）2]（PF 6）（2）和[DyIII（LN 6）（Ph 3SiO）2]（BPh 4）（3）六方双锥镝（III）单分子磁体（SMM），具有高各向异性势垒，在零外加直流场下，1的Ueff =973 K，2的Ueff=1080 K，3的Ueff =1124 K。从头计算预测，这些复合物的主要磁化反转势垒扩展到第三Kramers双重态，从而首次揭示了即使是六个赤道施主原子也无法消除的特殊单轴磁各向异性，为其他高阶对称性SMM开辟了可能性。
Following a novel synthetic strategy where the strong uniaxial ligand field generated by the Ph3SiO−(Ph3SiO−=anion of triphenylsilanol) and the 2,4‐di‐tBu‐PhO−(2,4‐di‐tBu‐PhO−=anion of 2,4‐di‐tertbutylphenol) ligands combined with the weak equatorial field of the ligandLN6, leads to [DyIII(LN6)(2,4‐di‐tBu‐PhO)2](PF6) (1), [DyIII(LN6)(Ph3SiO)2](PF6) (2) and [DyIII(LN6)(Ph3SiO)2](BPh4) (3) hexagonal bipyramidal dysprosium(III) single‐molecule magnets (SMMs) with high anisotropy barriers ofUeff=973 K for1,Ueff=1080 K for2andUeff=1124 K for3under zero applied dc field. Ab initio calculations predict that the dominant magnetization reversal barrier of these complexes expands up to the 3rd Kramers doublet, thus revealing for the first time the exceptional uniaxial magnetic anisotropy that even the six equatorial donor atoms fail to negate, opening up the possibility to other higher‐order symmetry SMMs.