| Homoleptic Fluoride Complexes as Modules for Molecular Spin-Architectures Kasper Pedersen1; 1TECHNICAL UNIVERSITY OF DENMARK, Lyngby, Denmark; PAPER: 397/Chemistry/Regular (Oral) SCHEDULED: 11:45/Sat. 26 Oct. 2019/Aphrodite A (100/Gr. F) ABSTRACT: Diffuse orbitals and large magnetic anisotropy resulting from strong spin-orbit coupling make complexes <sub></sub>with central ions from the 4d and 5d series interesting modules for magnetic materials [1]. The vast majority of molecule-based magnetic materials encompassing those elements utilize cyanide bridging. The common linearity of {M–CN–M} motifs is paralleled in fluoride-bridged systems, which thereby also proffers the desired synthetic handle in the design of new materials. When using simple [MF<sub>6</sub>]<sup>n–</sup> complexes as building blocks for complex architectures, the main obstacle is their common inherent lability outside hydrofluoric acid solutions, towards, for example, hydrolysis. This tendency is strongly diminished for several 4d and 5d [MF<sub>6</sub>]<sup>2–</sup> complexes and we herein present the use of [MF<sub>6</sub>]<sup>2–</sup> (M = Zr, Re, Ir, Os,…) anions, prepared by various fluorination routes, as modules for molecular magnetic systems of various dimensionality [2]. We also discuss the chemistry and potential of related 5f systems such as [UF<sub>6</sub>]<sup>2–</sup> [3]. The ability of fluoride to mediate significant exchange interactions dwarfs the coupling present in related cyanide-bridged systems. Conclusively, our results reveal structurally simple, robust and strongly anisotropic [MF<sub>6</sub>]<sup>2–</sup> complexes of the heavier transition elements to be unique and versatile building blocks for novel types of (magnetically interesting) molecular systems. References: [1] X.-Y. Wang, C. Avendano, K. R. Dunbar, Chem. Soc. Rev. 2011, 40, 3213. [2] (a) K. S. Pedersen et al. Angew. Chem. Int. Ed., 2014, 53, 1351; b) K. S. Pedersen et al. Nat. Commun. 2016, 7, 12195; c) K. S. Pedersen et al. Chem. Eur. J. 2017, 23, 11244. [3] K. S. Pedersen et al. Angew. Chem. Int. Ed. 2019, accepted. |
