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Low‐Coordinate Single‐Ion Magnets by Intercalation of Lanthanides into a Phenol Matrix
Author(s) -
Meng YinShan,
Xu Ling,
Xiong Jin,
Yuan Qiong,
Liu Tao,
Wang BingWu,
Gao Song
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201801223
Subject(s) - lanthanide , dysprosium , isostructural , chemistry , ligand (biochemistry) , crystallography , ion , intercalation (chemistry) , ionic radius , phenol , ligand field theory , inorganic chemistry , crystal structure , organic chemistry , biochemistry , receptor
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′‐ i Pr‐6′‐CHMe(CH 2 − )C 6 H 3 )C 6 H 3 O − ; 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.