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Ferromagnetic exchange interaction in a new Ir(IV)–Cu(II) chain based on the hexachloroiridate(IV) anion

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Abstract

The iridium(IV) complex (NBu4)2[IrCl6] (1) has been synthetised, characterised and used as a precursor to prepare the new chloro-bridged heterobimetallic IrIV–CuII chain of formula {IrCl5(μ-Cl)Cu(viim)4}n (2) [viim = 1-vinylimidazole]. The crystal structure and magnetic properties of 1 and 2 have been investigated. Both compounds crystallise in the monoclinic system with space group C2/c. Each IrIV ion in both 1 and 2 is six-coordinate and bonded to six chloride ions in a regular octahedral geometry. In compound 2, the CuII ion exhibits an axially elongated octahedron with four N atoms, from four monodentate viim ligands, that form the equatorial plane, and two chloride ions that occupy the axial positions. The way in which the anionic [IrCl6]2− units are arranged in the crystal packing of 1, well separated from each other by means of the bulky NBu4+ cations, avoids significant intermolecular Ir–Cl⋯Cl–Ir interactions. The crystal lattice of 2 shows adjacent IrIV–CuII chains that are connected through π⋯π stacking interactions, and are organized adopting perpendicular arrangements. The study of the magnetic properties of 1 and 2 through dc magnetic susceptibility measurements reveals that 1 shows magnetic behaviour typical of noninteracting mononuclear centres with S = 1/2, whereas 2 exhibits ferromagnetic exchange coupling between the CuII and IrIV metal ions linked through chloride ligands. In addition, ac magnetic susceptibility measurements show a field-induced slow relaxation of the magnetisation for 1, indicating single-ion magnet (SIM) behaviour for this mononuclear IrIV system.

Graphical abstract: Ferromagnetic exchange interaction in a new Ir(iv)–Cu(ii) chain based on the hexachloroiridate(iv) anion

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Publication details

The article was received on 12 Jul 2019, accepted on 09 Aug 2019 and first published on 09 Aug 2019


Article type: Paper
DOI: 10.1039/C9DT02884F
Dalton Trans., 2019, Advance Article

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    Ferromagnetic exchange interaction in a new Ir(IV)–Cu(II) chain based on the hexachloroiridate(IV) anion

    A. Sanchis-Perucho and J. Martínez-Lillo, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C9DT02884F

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