Halogen Bonding Channels for Magnetic Exchange in Cu(II) Complexes with 2,5‐Di(methylthio)‐1,3,4‐thiadiazole

Abstract

Copper(II) complexes with 2,5-bis(methylthio)-1,3,4-thiadiazole (tda) formulated as [Cu(tda)_n X₂ ] (n=2, X=Cl^- , Br^- , C₂ N₃ ^- ; n= 1, X=C₂ N₃ ^- ) have been isolated and fully characterized. The crystal structures of all compounds have been determined using single-crystal X-ray diffraction (SCXRD). A study of the magnetic susceptibility in the range 1.77-300 K has shown that magnetic properties of the [Cu(tda)₂ Cl₂ ] and [Cu(tda)₂ Br₂ ] complexes match those of 1D chains of antiferromagnetically-coupled Cu²⁺ ions. The intrachain interaction J in [Cu(tda)₂ Cl₂ ] turns out to be ∼1.2 times weaker than in its bromide analogue. In its turn, [Cu(tda)₂ (C₂ N₃ )₂ ] exhibits J being an order of magnitude smaller and of the opposite ferromagnetic sign. Halogen bonding (HB) between adjacent complexes is much stronger than the H-bonds or π-π interactions between tda ligands according to the DFT calculations.