Access to Heteroleptic Fluorido-Cyanido Complexes with a Large Magnetic Anisotropy by Fluoride Abstraction

Jun-Liang Liu, Kasper Steen Pedersen, Samuel M Greer, Itziar Oyarzabal, Abhishake Mondal, Stephen Hill, Fabrice Wilhelm, Andrei Rogalev, Alain Tressaud, Etienne Durand, Jeffrey R Long, Rodolphe Clérac*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

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.
Original languageEnglish
JournalAngewandte Chemie International Edition
Number of pages6
ISSN1433-7851
DOIs
Publication statusAccepted/In press - 2020

Cite this

Liu, J-L., Pedersen, K. S., Greer, S. M., Oyarzabal, I., Mondal, A., Hill, S., Wilhelm, F., Rogalev, A., Tressaud, A., Durand, E., Long, J. R., & Clérac, R. (Accepted/In press). Access to Heteroleptic Fluorido-Cyanido Complexes with a Large Magnetic Anisotropy by Fluoride Abstraction. Angewandte Chemie International Edition. https://doi.org/10.1002/anie.201914934