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Access to Heteroleptic Fluorido‐Cyanido Complexes with a Large Magnetic Anisotropy by Fluoride Abstraction
Author(s) -
Liu JunLiang,
Pedersen Kasper S.,
Greer Samuel M.,
Oyarzabal Itziar,
Mondal Abhishake,
Hill Stephen,
Wilhelm Fabrice,
Rogalev Andrei,
Tressaud Alain,
Durand Etienne,
Long Jeffrey R.,
Clérac Rodolphe
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201914934
Subject(s) - homoleptic , chemistry , magnetization , magnetic anisotropy , anisotropy , fluoride , octahedron , crystallography , transition metal , molecule , electron paramagnetic resonance , metal , inorganic chemistry , nuclear magnetic resonance , magnetic field , organic chemistry , crystal structure , catalysis , physics , quantum mechanics
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 ‐[M IV F 4 (CN) 2 ] 2− (M=Re, Os), obtained from their homoleptic [M IV F 6 ] 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 ‐[ReF 4 (CN) 2 ] 2− as compared to [ReF 6 ] 2− , reflecting the severe departure from an ideal octahedral (O h 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.