Three types of charged ligand-based neutral phosphorescent iridium(III) complexes featuring nido-carborane: synthesis, structures, and solution processed organic light-emitting diode applications

In view of the fact that coordination configurations and special functional groups are both important for the optical properties of phosphorescent iridium complex materials, we have prepared a novel family of three types of charged ligand (0, -1, and -2) based neutral phosphorescent iridium(III) complexes (Ir1-Ir4) featuring nido-carborane. Single crystal structures indicate that complexes (Ir2, Ir3 and Ir4) with nido-carborane as a functional group at different substitution sites all show a trans-C<^>C configuration between dianionic (-2) and monoanionic (-1) ligands, which are different from the trans-N<^>C configuration in complex Ir1 with nido-carborane as a coordination skeleton, which has an interesting Ir-B coordination bond. Notably, Ir2, Ir3 and Ir4 all show obvious yellow light emission, while Ir1 does not emit light either in solution or in the solid state. DFT calculations demonstrate that complexes Ir2, Ir3 and Ir4 exhibit an unusual ligand-to-metal charge transfer (LMCT) excited state character due to the strong electron-donating character of nido-carborane. Considering its better solubility and luminescence properties, Ir3 was successfully applied in solution-processed organic light-emitting diodes and an effective yellow emission was achieved. This work provides a new strategy for the investigation of three types of charged ligand (0, -1, and -2) based phosphorescent iridium complex materials by constructing new dianionic ligands with nido-carborane.