On-complex three-component cascade reactions involving phosphorescent cyclometalated Ir(iii) chloro-isocyanide complexes, nitriles, and propylamine.

An "on-complex" three-component cascade reaction involving cyclometalated iridium chloro-isocyanide complexes, nitriles, and propylamine is reported. This ligand-based functionalization approach gives access to phosphorescent bis-cyclometalated iridium compounds containing a new chelating imino-acyclic diamino carbene (imino-ADC) ligand, not accessible by traditional organometallic synthesis. The reaction is compatible with alkyl nitriles and iridium complexes bearing different cyclometalating ligands and aromatic isocyanides. The imino-ADC ligand in the resulting cationic products can be deprotonated in a separate step to give the corresponding neutral compounds. The products of the cascade reactions were obtained in low to moderate yields, depending on the isocyanide and nitrile substituents used, with their structures characterized by multinuclear NMR and single-crystal X-ray diffraction. Photophysical measurements show that the complexes described here exhibit blue phosphorescence, with the spectral profile dependent on the cyclometalating ligand, which is either 2,4-difluorophenylpyridine (F