TY - JOUR TI - Cyclometalated N-heterocyclic carbene iridium(III) complexes with naphthalimide chromophores: a novel class of phosphorescent heteroleptic compounds AU - Lanoë, Pierre-Henri AU - Chan, Jonny AU - Groué, Antoine AU - Gontard, Geoffrey AU - Jutand, Anny AU - Rager, Marie-Noelle AU - Armaroli, Nicola AU - Monti, Filippo AU - Barbieri, Andrea AU - Amouri, Hani T2 - Dalton Transactions AB - 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 3MLCT to 3LC, 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 knr 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. DA - 2018/03/06/ PY - 2018 DO - 10.1039/C7DT04369D DP - pubs.rsc.org VL - 47 IS - 10 SP - 3440 EP - 3451 J2 - Dalton Trans. LA - en SN - 1477-9234 ST - Cyclometalated N-heterocyclic carbene iridium(III) complexes with naphthalimide chromophores UR - https://pubs.rsc.org/en/content/articlelanding/2018/dt/c7dt04369d Y2 - 2018/12/20/15:05:14 KW - ARC KW - POLE 1 ER -