Halide-Enhanced Spin–Orbit Coupling and the Phosphorescence Rate in Ir(III) Complexes

The spin-forbidden nature of phosphorescence in Ir­(III) complexes is relaxed by the metal-induced effect of spin–orbit coupling (SOC). A further increase of the phosphorescence rate could potentially be achieved by introducing additional centers capable of further enhancing the SOC effect, such as metal-coordinated halides. Herein, we present a dinuclear Ir­(III) complex Ir 2 I 2 that contains two Ir­(III)-iodide moieties. The complex shows intense phosphorescence with a quantum yield of ΦPL(300 K) = 90% and a submicrosecond decay time of only τ­(300 K) = 0.34 μs, as measured under ambient temperature for the degassed toluene solution. These values correspond to a top value T1 → S0 phosphorescence rate of k r = 2.65 × 106 s–1. Investigations at cryogenic temperatures allowed us to determine the zero-field splitting (ZFS) of the emitting state T1 ZFS­(III–I) = 170 cm–1 and unusually short individual decay times of T1 substates: τ­(I) = 6.4 μs, τ­(II) = 7.6 μs, and τ­(III) = 0.05 μs. This indicates a strong SOC of state T1 with singlet states. Theoretical investigations suggest that the SOC of state T1 with singlets is also contributed by halides. Strongly contributing to the higher occupied molecular orbitals of the complex (e.g., HOMO, HOMO – 1, and so forth), iodides work as important SOC centers that operate in tandem with metals. The examples of Ir 2 I 2 and of earlier reported analogous complex Ir 2 Cl 2 reveal that the metal-coordinated halides can enhance the SOC of state T1 with singlets and, consequently, the phosphorescence rate. A comparative study of Ir 2 I 2 and Ir 2 Cl 2 shows that the share of halides in total contribution (halides plus metals) to the SOC of state T1 with singlets increases strongly upon exchange of chlorides for iodides. The exchange also led to the decrease in values of ZFS of the T1 state from ZFS­(III–I) = 205 cm–1 for Ir 2 Cl 2 to T1 ZFS­(III–I) = 170 cm–1 for Ir 2 I 2 . This results in a more efficient thermal population of the fastest emitting T1 substate III, thus further enhancing the room-temperature phosphorescence rate.