Cyclometalated N-heterocyclic carbene iridium(III) complexes with naphthalimide chromophores: a novel class of phosphorescent heteroleptic compounds

A series of cyclometalated N-heterocyclic carbene complexes of the general formula [Ir(C<^>N)(2)(C<^>C:)] has been prepared. Two sets of compounds were designed, those where (C<^>C:) represents a bidentate naphthalimide-substituted imidazolylidene ligand and (C<^>N) = ppy (3a), F2ppy (4a), bzq (5a) and those where (C<^>C:) represents a naphthalimide-substituted benzimidazolylidene ligand and (C<^>N) = ppy (3b), F2ppy (4b), bzq (5b). The naphthalimide-imidazole and naphthalimide-benzimidazole ligands 1a,b and the related imidazolium and benzimidazolium salts 2a, b were also prepared and fully characterized. The N-heterocyclic carbene Ir(III) complexes have been characterized by NMR spectroscopy, cyclic voltammetry and elemental analysis. Moreover, the molecular structures of one imidazolium salt and four Ir(III) complexes were determined by single-crystal X-ray diffraction. The structures provide us with valuable information, most notably the orientation of the naphthalimide chromophore with respect to the N-heterocyclic carbene moiety. All compounds are luminescent at room temperature and in a frozen solvent at 77 K, exhibiting a broad emission band that extends beyond 700 nm. The presence of the naphthalimide moiety changes the character of the lowest excited state from (MLCT)-M-3 to (LC)-L-3, as corroborated by DFT and TD-DFT calculations. Remarkably, replacing imidazole with a benzimidazole unit improves the quantum yields of these compounds by decreasing the k(nr) values which is an important feature for optimized emission performance. These studies provide valuable insights about a novel class of N-heterocyclic carbene-based luminescent complexes containing organic chromophores and affording metal complexes emitting across the red-NIR range.