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

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

doi:10.1002/anie.201914934

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

Angew Chem Int Ed Engl. 2020 Jun 22;59(26):10306-10310. doi: 10.1002/anie.201914934. Epub 2020 Apr 15.

Authors

Jun-Liang Liu^{1

2}, Kasper S Pedersen^{1

3}, Samuel M Greer^{4

5}, Itziar Oyarzabal^{1

6}, Abhishake Mondal^{1

7}, Stephen Hill^{8

5}, Fabrice Wilhelm⁹, Andrei Rogalev⁹, Alain Tressaud¹⁰, Etienne Durand¹⁰, Jeffrey R Long^{11

12

13}, Rodolphe Clérac¹

Affiliations

¹ Univ. Bordeaux, CNRS, Centre de Recherche Paul Pascal, CRPP, UMR 5031, 33600, Pessac, France.
² Current address: Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, P. R. China.
³ Current address: Department of Chemistry, Technical University of Denmark, 2800, Kgs., Lyngby, Denmark.
⁴ Department of Chemistry, Florida State University.
⁵ National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL, 32306, USA.
⁶ Chemistry Faculty, University of the Basque Country UPV/EHU, 20018, Donostia-San Sebastián, Spain.
⁷ Current address: Solid State and Structural Chemistry Unit, Indian Institute of Science, C.V. Raman Road, Bangalore, 560012, India.
⁸ Department of Physics, Florida State University.
⁹ ESRF-The European Synchrotron, 38043, Grenoble Cedex 9, France.
¹⁰ CNRS, ICMCB, UPR 9048, Univ. Bordeaux, 33608, Pessac, France.
¹¹ Department of Chemistry, University of California Berkeley, USA.
¹² Department of Chemical and Biomolecular Engineering, University of California Berkeley, USA.
¹³ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.

PMID: 32080955
DOI: 10.1002/anie.201914934

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-[M^IV F₄ (CN)₂ ]^2- (M=Re, Os), obtained from their homoleptic [M^IV 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 (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.

Keywords: cyanides; electron paramagnetic resonance; fluorides; magnetic anisotropy; single-molecule magnets.

Abstract

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