Aligning ?-Extended ?-Deficient Ligands to Afford Submicrosecond Phosphorescence Radiative Decay Time of Mononuclear Ir(III) Complexes

Herein, we report a profound investigation of the photo-physical properties of three mononuclear Ir(III) complexes fac-Ir(dppm)3 (Hdppm-4,6-bis(4-(tert-butyl)phenyl)pyrimidine), Ir(dppm)2(acac) (acac- acetylacetonate), and Ir(ppy)2(acac) (Hppy-phenylpyridine). The hetero-leptic Ir(dppm)2(acac) is found to emit with efficiency above 80% and feature a remarkably high rate of emission. As measured under ambient temperature, Ir(dppm)2(acac) emits with the unusually short (sub-mu s) radiative decay time of tau r = tau em/phi PL = 1/kr = 0.91 mu s in degassed toluene and tau r = 0.73 mu s in a doped polystyrene film under nitrogen. Investigations at cryogenic temperatures in glassy toluene showed that the emission stems from the T1 state and thus represents T1 -> S0 phosphorescence with individual decay times of the T1 substates of T1,I = 66 mu s, T1,II = 7.3 mu s, T1,III= 0.19 mu s, and energy gaps between the substates of Delta E(T1,II-T1,I) = 14 cm-1 and Delta E(T1,III-T1,I) = 210 cm-1. Analysis of the electronic structure of Ir(dppm)2(acac) showed that such a high rate of phosphorescence may stem from the two dppm ligands, with extended pi-conjugation system and pi-deficient character due to the pyrimidine ring, being serially aligned along one axis. Such alignment, along with the quasi-symmetric character of Jahn- Teller distortions in the T1 state, affords a large chromophore, comprising four (het)aryl rings of the two dppm ligands. This affords an exceptionally large oscillator strength of the MLCT-character singlet state spin-orbit coupled with the T1 state and thus brings about enhancement of the phosphorescence rate. These findings reveal molecular design principles paving the way to new phosphors of enhanced emission rates.

Automated summary

We investigated the photo-physical properties of three mononuclear Ir(III) complexes fac-Ir(dppm)3, Ir(dppm)2(acac), and Ir(ppy)2(acac). Among them, Ir(dppm)2(acac) showed high emission efficiency and a remarkably short radiative decay time. Our analysis of the electronic structure revealed that the high phosphorescence rate of Ir(dppm)2(acac) is attributed to the alignment of the dppm ligands and the large chromophore formed by the (het)aryl rings. These findings provide molecular design principles for developing phosphors with enhanced emission rates.