Unusually Fast Phosphorescence from Ir(III) Complexes via Dinuclear Molecular Design

The design and detailed photophysical study of two novel Ir(III) complexes featuring mono- and dinuclear design are presented. Emission quantum yield and decay times in solution are Φ_PL = 90% and τ(300 K) = 1.16 μs for the mononuclear complex 5, and Φ_PL = 95% and τ(300 K) = 0.44 μs for the dinuclear complex 6. These data indicate an almost 3-fold increase in the phosphorescence rate for dinuclear complex 6 compared to 5. Zero-field splitting (ZFS) of the T₁ state also increases from ZFS = 65 cm^-1 for the mononuclear complex to ZFS = 205 cm^-1 for the dinuclear complex and is accompanied by a drastic shortening of the individual decay times of T₁ substates. With the help of TD-DFT calculations, we rationalize that the drastic changes in the T₁ state properties in the dinuclear complex originate from an increased number of excited states available for direct spin-orbit coupling (SOC) routes as a result of electronic coupling of Ir-Cl antibonding molecular orbitals of the two coordination sites.