Non-Stereogenic Dinuclear Ir(III) Complex with a Molecular Rack Design to Afford Efficient Thermally Enhanced Red Emission.

Cyclometalated complexes containing two or more metal centers were recently shown to offer photophysical properties that are advantageous compared to their mononuclear analogues. Here we report the design, synthesis, and luminescent properties of a dinuclear Ir(III) complex formed by a ditopic NCN-NCN bridging ligand (L) with pyrimidine as a linking heterocycle. Two dianionic CNC terminal ligands were employed to achieve a charge-neutral and nonstereogenic dinuclear complex . This complex shows a highly efficient red emission with a maximum at λ = 642 nm as measured for a toluene solution. The decay time and emission quantum yield of the complex measured for the degassed sample are τ = 1.31 μs and Φ = 80%, respectively, corresponding to the radiative rate of = 6.11·10 s. This rate value is approximately fourfold faster than for the green-emitting mononuclear analogue . Cryogenic temperature measurements show that the three substrates of the lowest triplet state T of emit with decay times of τ(I) = 120 μs, τ(II) = 7 μs, and τ(III) = 1 μs that are much shorter compared to those of the mononuclear complex , which has values of τ(I) = 192 μs, τ(II) = 65.6 μs, and τ(III) = 3.6 μs. These data indicate that the spin-orbit coupling of state T with the singlet states is much stronger in the case of complex , which results in a much higher T → S emission rate. Indeed, a computational analysis suggests that in the dinuclear complex the T state is spin-orbit coupled with twice the number of singlet states compared to that of mononuclear , which is a result of the electronic coupling of two coordination sites. The investigation of the temperature dependence of the emission rates of and shows that the room-temperature emission of both complexes is mainly contributed by a thermally populated excited state lying above the T state. To the best of our knowledge, complexes and are the first examples of Ir(III) complexes that show photophysical behavior reminiscent of thermally activated delayed fluorescence (TADF).