Halogen bonded metal bis(dithiolene) 2D frameworks

Abstract

Halogenated metal dithiolene complexes have been designed together with halogen bond acceptor sites in order to favor halogen bonding interactions between these electroactive architectures. For the synthesis, we explored the reactivity of the protected N-tert-butyl-1,3-thiazoline-2-thione-4,5-dithiolate ligand towards DMSO and I₂ and successfully prepared the appropriate protected 2-iodo-1,3-thiazole-4,5-dithiolate ligand, (I-tzdt). Nickel and gold monoanionic complexes, [M(I-tzdt)₂]⁻¹ (M = Au, Ni), have been synthesized and the Au complexes were isolated in the solid state in their trans and cis isomers. The trans-Ni and trans-Au complexes are isostructural and X-ray diffraction analysis confirmed the occurrence of short and directional I⋯S halogen bonding interactions leading to 2D metal bis(dithiolene) frameworks with channels hosting the counterions. On the other hand, additional chalcogen⋯chalcogen interactions are observed for the cis-Au complex, transforming the 2D into a 3D network.