A new family of one-dimensional bromo-bridged Ir(iv)–Cu(ii) complexes based on the hexabromoiridate(iv) metalloligand

Abstract

By using the iridium(IV) complex (NBu₄)₂[IrBr₆] (1) as a metalloligand towards a Cu(II) metal ion, three novel Ir(IV) one-dimensional (1D) compounds of formula {IrBr₅(μ-Br)Cu(Meim)₄}_n (2), {IrBr₅(μ-Br)Cu(Viim)₄}_n (3) and {IrBr₅(μ-Br)Cu(Buim)₄}_n (4), [Meim = 1-methylimidazole; Viim = 1-vinylimidazole; Buim = 1-butylimidazole] have been prepared and structurally and magnetically characterised. Compounds 2, 3 and 4 crystallise in the triclinic, monoclinic and orthorhombic crystal systems with space groups P, C2/c and Pccn, respectively. Each Ir(IV) ion in 1–4 is six-coordinate and bonded to six bromide ions in a quasi regular octahedral geometry. In compounds 2–4, the Cu^II ion shows an axially elongated octahedron with four N atoms, from four monodentate imidazole derivative ligands, that form the equatorial plane and two bromide ions that occupy the axial positions. Cu(II) and Ir(IV) ions are linked through bridging bromide anions generating Ir(IV)–Cu(II) chains [with intrachain Cu(II)⋯Ir(IV) distances covering the range of ca. 5.10–5.42 Å]. In the crystal lattice of 2 and 3 are observed significant intermolecular Ir–Br⋯Br–Ir contacts and π⋯Br interactions, which organize arrangements that contribute to stabilizing the crystal structure of these Ir(IV)-based compounds. DC magnetic susceptibility measurements reveal that 1 displays magnetic behaviour typical of noninteracting mononuclear centres with S = 1/2. Besides, antiferromagnetic behaviour (2 and 3) and ferromagnetic (4) exchange coupling occur between the Cu(II) and Ir(IV) metal ions in the one-dimensional bromo-bridged compounds 2–4. Moreover, the study of the AC magnetic susceptibility shows a field-induced slow relaxation of the magnetisation for 1, indicating the presence of the single-ion magnet (SIM) phenomenon for the magnetically isolated hexabromoiridate(IV) complex.