Fluorescent phenoxy benzoxazole complexes of zirconium and hafnium: synthesis, structure and photo-physical behaviour

A series of ten heteroleptic and homoleptic mononuclear Zr(iv) and Hf(iv) complexes bearing differently substituted phenoxy-benzoxazole ligands was synthesised. The complexes were characterised by 1H and 13C{1H} NMR spectroscopy as well as by elemental analyses and X-ray diffraction experiments. The molecular structures show octahedral or tetragonal-antiprismatic coordination motifs at the metal atom. The crystal packing patterns depend on the substitution of the ligands. The intermolecular interactions in the solid state are governed by weak π-π interactions, and are also dependent on the ligand structure. Photo-physical investigations reveal that all ten complexes show a ligand-centered fluorescence with emission maxima in the blue region of the electromagnetic spectrum.