TY - JOUR
T1 - Access to Heteroleptic Fluorido-Cyanido Complexes with a Large Magnetic Anisotropy by Fluoride Abstraction
AU - Liu, Jun-Liang
AU - Pedersen, Kasper Steen
AU - Greer, Samuel M
AU - Oyarzabal, Itziar
AU - Mondal, Abhishake
AU - Hill, Stephen
AU - Wilhelm, Fabrice
AU - Rogalev, Andrei
AU - Tressaud, Alain
AU - Durand, Etienne
AU - Long, Jeffrey R
AU - Clérac, Rodolphe
PY - 2020
Y1 - 2020
N2 - Silicon-mediated fluoride abstraction is demonstrated as a means of generating the first fluorido-cyanido transition metal complexes. This new synthetic approach is exemplified by the synthesis and characterization of the heteroleptic complexes, trans-[MIV F4 (CN)2 ]2- (M=Re, Os), obtained from their homoleptic [MIV F6 ]2- parents. As shown by combined high-field electron paramagnetic resonance spectroscopy and magnetization measurements, the partial substitution of fluoride by cyanide ligands leads to a marked increase in the magnetic anisotropy of trans-[ReF4 (CN)2 ]2- as compared to [ReF6 ]2- , reflecting the severe departure from an ideal octahedral (Oh point group) ligand field. This methodology paves the way toward the realization of new heteroleptic transition metal complexes that may be used as highly anisotropic building-blocks for the design of high-performance molecule-based magnetic materials.
AB - Silicon-mediated fluoride abstraction is demonstrated as a means of generating the first fluorido-cyanido transition metal complexes. This new synthetic approach is exemplified by the synthesis and characterization of the heteroleptic complexes, trans-[MIV F4 (CN)2 ]2- (M=Re, Os), obtained from their homoleptic [MIV F6 ]2- parents. As shown by combined high-field electron paramagnetic resonance spectroscopy and magnetization measurements, the partial substitution of fluoride by cyanide ligands leads to a marked increase in the magnetic anisotropy of trans-[ReF4 (CN)2 ]2- as compared to [ReF6 ]2- , reflecting the severe departure from an ideal octahedral (Oh point group) ligand field. This methodology paves the way toward the realization of new heteroleptic transition metal complexes that may be used as highly anisotropic building-blocks for the design of high-performance molecule-based magnetic materials.
U2 - 10.1002/anie.201914934
DO - 10.1002/anie.201914934
M3 - Journal article
C2 - 32080955
SN - 1433-7851
VL - 56
SP - 10306
EP - 10310
JO - Angewandte Chemie International Edition
JF - Angewandte Chemie International Edition
IS - 26
ER -