Photoluminescent organoplatinum (II) complexes containing N-heterocyclic carbene (NHC) ligands

Abstract

The syntheses, structures, photophysical properties and applications of three types of photoluminescent organoplatinum(II) complexes containing N-heterocyclic carbene (NHC) ligands are described. The tetradentate dianionic bis(phenolate-NHC) type ligands provide a superior scaffold for constructing thermally stable and efficient deep-blue phosphorescent Pt(II) complexes with λmax of ~440-460 nm and solid-state emission quantum yields of ~30%. Highly efficient blue OLEDs with CIEx, y of (0.19, 0.21) were fabricated based on these emitters with maximum brightness, peak current efficiency and power efficiency of ~9500 cd m^(-2), 24 cd A^(-1) and 17 lm W^(-1), respectively. Structural modification by extending the π-conjugation of the tetradentate bis(phenolate-NHC) ligand leads to strongly phosphorescent platinum(II) complexes with long-lived emissive electronic states that can be used as a luminescent sensor for oxygen. DFT/TDDFT calculations and time-resolved spectroscopic characterizations were performed to gain insight into the structure-photophysics correlation. The N-heterocyclic carbene (NHC) ligand was incorporated into Pt(II) complexes containing tridentate deprotonated 1,3-bis(2-pyridyl)benzene (N^C^N) type ligand. In addition to the [(N^C^N)Pt(NHC)]PF6 type complexes with (N^C^N) in η3-tridentate coordination mode, Pt(II) complexes with η2-bidentate (N^CN) ligands, namely [(N^CN)Pt(NHC)2]PF6, have been isolated and structurally characterized. The highly phosphorescent [(N^C^N)Pt(NHC)]PF6 complexes were used for solution-processed green OLEDs fabrication. The peak current efficiency of 12.5 cd A^(-1) and maximum brightness higher than 2000 cd m^(-2) were achieved. The presence of the pendent pyridyl motif causes quenching of emission of the [(N^CN)Pt(NHC)2]PF6 complexes in solution at room temperature. Turning on solid-state emission of [(N^CN)Pt(nBu2Im)2]PF6 in the presence of an acidic vapor revealed its potential as a luminescent chemosensor. A class of dicationic platinum(II) terpyridyl complexes containing NHC ligand, namely [Pt(tpy)(NHC)](PF6)2, has been synthesized and structurally characterized. Even in the presence of the strong σ-donating NHC ligand, these complexes are non- or weakly emissive in solution at room temperature. However, this class of complexes displays intense emissions in solid state (298 K and 77 K), in glassy solution (77 K butyronitrile) and in PMMA (2 wt.%, 298 K). The ligand (terpyridine) displacement reaction arising from CN attack onto the Pt(II) center has been observed for [Pt(tpy)(nBu2Im)](PF6)2 leading to its application as a chemodosimeter for selective cyanide sensing in aqueous solution.