Low‐Coordinate Single‐Ion Magnets by Intercalation of Lanthanides into a Phenol Matrix,Angewandte Chemie International Edition

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Low‐Coordinate Single‐Ion Magnets by Intercalation of Lanthanides into a Phenol Matrix
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-03-15 , DOI: 10.1002/anie.201801223
Yin-Shan Meng ₁ , Ling Xu ₂ , Jin Xiong ₃ , Qiong Yuan ₃ , Tao Liu ₁ , Bing-Wu Wang ₃ , Song Gao ₃

Affiliation

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‐Dipp₂C₆H₃, Dipp=2,6‐diisopropylphenyl) was utilized to construct low‐coordinate lanthanide compound [(ArO)Ln(OAr′)] (Ar′=6‐Dipp‐2‐(2′‐ⁱPr‐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.

中文翻译：

通过将镧系元素插入苯酚基体中的低配位单离子磁体

合成稳定的三价稀土配合物非常困难，其中高氧化态的配位数低于3，离子半径大，三价镧系离子几乎没有键合特性。庞大的酚配体ArOH（Ar = 2,6-Dipp ₂ C ₆ H ₃，Dipp = 2,6-二异丙基苯基）被用于构建低配位镧系元素化合物[（ArO）Ln（OAr'）]（Ar'= 6‐Dipp‐2‐（2′ ‐ ⁱ Pr‐6′‐CHMe（CH ₂⁻）C ₆ H ₃）C ₆ H ₃ O ⁻; Ln = Tb，Dy，Ho，Er，Tm）。这些络合物和游离配体ArOH是同构的。磁性测量和理论研究表明，扁圆形的s和扁圆形的analogue类似物均表现出单离子磁体（SIM）的行为。庞大的酚配体提供了强大的单轴配体场，使SIM SIM具有高达961 K的阻断势垒。

更新日期：2018-03-15

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