Neutral 2-phenylbenzimidazole-based iridium() complexes with picolinate ancillary ligand: tuning the emission properties by manipulating the substituent on the benzimidazole ring

We report the synthesis and characterization of ten neutral bisheteroleptic iridium( iii ) complexes with 2-phenylbenzimidazole cyclometallating ligand and picolinate as ancillary ligand. The 2-phenylbenzimidazole has been modified by selected substituents introduced on the cyclometallating ring and/or on the benzimidazole moiety. The integrity of the complexes has been assessed by NMR spectroscopy, by high-resolution mass spectrometry and by elemental analysis. The complexes are demonstrated to be highly phosphorescent at room temperature and a luminescence study with comprehensive ab initio calculations allow us to determine the lowest emitting excited state which depends on the substituent nature and its position on the cyclometallating ligand. A luminescence study with ab initio calculations that allow us to determine the lowest emitting excited state of a series of neutral Ir( iii ) complexes with 2-phenylbenzimidazole cyclometallating ligand.