Synthesis, structure and optoelectronic properties of iridium(III) complexes bearing a four-membered Ir-N-C[sbnd]N chelate structure

Abstract

Herein four novel iridium(III) complexes (tfpmd)2Ir(dpppy) (Ir1a, tfpmd = 2-(4-(trifluoromethyl) phenyl) pyrimidine, dpppy = P,P-diphenyl-N-(pyridin-2-yl)phosphinic amide), (tfpmd)2Ir(dppq) (Ir1b, dppq = P,P-diphenyl-N-(quinolin-2-yl)phosphinic amide), (tfpqz)2Ir(dpppy) (Ir2a, tfpzq = 4-(4-(trifluoromethyl) phenyl) quinazoline) and (tfpqz)2Ir(dppq) (Ir2b) were synthetized, and their structures, opto-physical, and electro-chemical properties were investigated in detail. The crystal structure shows that these complexes exhibit pseudo-octahedral geometry around iridium atom coordinated by C, N atoms from cyclometalated and ancillary ligands. Interestingly, two coordinated nitrogen atoms from the ancillary ligand form an unusual quaternary ring with the central iridium ion. Ir1a and Ir1b emit pure-green light with Commission Internationale de L'Eclairage (CIE) color coordinates of (0.25, 0.67) and (0.22, 0.67), respectively, in CH2Cl2 solution. With the increase of the degree of conjugation of the cyclometalated ligand from tfpmd to tfpqz, the luminescence of complexes Ir2a and Ir2b is greatly red-shifted, and pure-red emission with CIE coordinates of (0.66, 0.34) and (0.66, 0.34), respectively, is obtained. The photophysical behaviors were reasonably explained by quantum chemical calculations. The calculation results shows that their emission is ascribed to the mixed 3MLCT (metal-ligand charge transfer, dπ(Ir)→π*(cyclometalated ligand)) and 3LLCT (ligand-ligand charge transfer, π(ancillary ligand)→π*(cyclometalated ligand)) states. Owing to their good thermal and electrochemical stabilities, organic light emitting diode (OLED) devices with dual-emitting layer structure and a space interlayer were fabricated and exhibited high electroluminescent properties and mild efficiency roll-off (14%-21%).