Low-Coordinate Single-Ion Magnets by Intercalation of Lanthanides into a Phenol Matrix
Low-Coordinate Single-Ion Magnets by Intercalation of Lanthanides into a Phenol Matrix
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DOI：
10.1002/anie.201801223
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发表时间：
2018-04-16
影响因子：
16.6
通讯作者：
Gao, Song
中科院分区：
文献类型：
--
作者：
Meng, Yin-Shan;Xu, Ling;Gao, Song
由于三价稀土离子的高氧化态、大离子半径和几乎不成键的特点，合成稳定的三价稀土配合物具有很大的挑战性。利用大体积酚类配体ArOH（Ar = 2，6-Dipp（2）C（6）H（3），Dipp = 2，6-二异丙基苯基）构建了低配位镧系化合物[（ArO）Ln-（OAr '）]（Ar' = 6-Dipp-2-（2 '-Pr-i-6-CHMe（CH 2-）C6 H3）-C6 H3 O-; Ln = Tb，Dy，Ho，Er，Tm）.这些配合物和自由配体ArOH是同构的。磁性测量和理论研究表明，扁长型镝和扁长型铒类似物都表现出单离子磁体（SIM）行为。大体积的酚类配体提供了强的单轴配位场，使镝SIM在961 K具有阻断势垒。
It is very challenging to synthesize stable trivalent rare-earth complexes in which the coordination number is lower than 3 for the high oxidation state, there is a large ion radius and nearly non-bonding character of trivalent lanthanide ions. The bulky phenol ligand ArOH (Ar = 2,6-Dipp(2)C(6)H(3), Dipp = 2,6-diisopropylphenyl) was utilized to construct low-coordinate lanthanide compound [(ArO)Ln-(OAr')] (Ar' = 6-Dipp-2-(2'-Pr-i-6-CHMe(CH2-)C6H3)-C6H3O-; Ln = Tb, Dy, Ho, Er, Tm). These complexes and the free ligand ArOH were isostructural. Magnetic measurements and theoretical studies demonstrated that both the oblate-type dysprosium and prolate-type erbium analogues exhibited single-ion magnet (SIM) behavior. The bulky phenol ligands provided strong uniaxial ligand field, making the dysprosium SIM possessing blocking barrier up to 961 K.