Tridentate complexes of group 10 bearing bis-aryloxide N-heterocyclic carbene ligands: Synthesis, structural, spectroscopic, and computational characterization

A series of group 10 complexes featuring chelating tridentate bis-aryloxide N-heterocyclic carbenes were synthesized and characterized by using different techniques. Ni(II), Pd(II), and Pt(II) complexes were isolated in good yields by straightforward direct metalation of the corresponding benzimidazolium or imidazolium precursors in a one-pot procedure. All of the compounds were fully characterized, including single-crystal X-ray diffractometric determination for three of the derivatives. In the solid state, the complexes adopt a typical square-planar coordination geometry around the platinum atom, sizably distorted in order to comply with the geometrical constraints imposed by the bis-aryloxide N-heterocyclic carbene ligand. For platinum and palladium derivatives, a joint experimental and theoretical characterization was performed in order to study the optical properties of the newly prepared complexes by means of electronic absorption and steady-state and time-resolved photophysical techniques as well as density functional theory (DFT) and time-dependent DFT in both vacuum and solvent. When the temperature was lowered to 77 K in frozen glassy matrix, three platinum complexes showed broad and featureless, yet weak, photoluminescence in the green region of the visible spectrum with excited-state lifetimes on the order of a few microseconds. On the basis of joint experimental and computational findings and literature on platinum complexes, such emission was assigned to a triplet-manifold metal-ligand-to-ligand charge transfer (3MLLCT) transition