Carbazolylpyridine (cp)-based tetradentate platinum(II) complexes containing fused 6/5/6 metallocycles.

A series of carbazolylpyridine (cp)-based 6/5/6 Pt(II) complexes featuring tetradentate ligands with nitrogen or oxygen atoms as bridging groups was designed and synthesized, and the bridging nitrogen atoms were derived from acridinyl (Ac), azaaceridine (AAc) and carbazole (Cz). Systematic experimental and theoretical studies reveal that the ligand structures have a significant effect on the electrochemical, photophysical and excited state properties of these complexes. Their oxidation processes mainly occur on the carbazole-Pt moieties, whereas the reduction processes typically occur on the electron-deficient pyridine (Py) moieties. Time-dependent density functional theory (TD-DFT) and natural transition orbital (NTO) calculations reveal that the cp-based Pt(II) complexes have a metal-to-ligand charge transfer (3MLCT) state mixed with ligand-centered (3LC) and intra-ligand charge-transfer (3ILCT) characteristics. Pt(cp-1) shows strong red luminescence with a dominant peak at 611 nm and an excited-state lifetime of 10.7 μs in dichloromethane at room temperature, 602 nm and 10.9 μs in toluene, and 602 nm and 8.2 μs in PMMA films. It also exhibits high photoluminescence quantum efficiencies of 85%, 84% and 60% in dichloromethane, toluene and PMMA, respectively. These studies indicate the potential application of the cp-based Pt(II) complexes as phosphorescent emitters in the field of organic light-emitting diodes (OLEDs).