Deep Blue Phosphorescence from Platinum Complexes Featuring Cyclometalated N-Pyridyl Carbazole Ligands with Monocarborane Clusters (CB11H12–)

The utilization of deep blue phosphorescent materials in high-performance displays and solid-state lighting requires high quantum efficiencies and color purities. Here, we describe the preparation and luminescent properties of novel platinum triplet emitters featuring cyclometalated N-pyridyl-carbazole ligands functionalized with closo-monocarborane clusters [CB11H12]-. All reported complexes were fully characterized by using standard small molecule techniques (UV-vis, cyclic voltammetry, nuclear magnetic resonance (NMR), high-resolution mass spectrometry (HRMS)), and their solid-state structures were elucidated by X-ray diffraction. These platinum phosphors emit in the blue region of the visible wavelength spectrum in both the solid and solution states. Complex 4a exhibits the highest luminous efficiency at λem = 439 nm with a photoluminescent quantum yield (PLQY) of 60% by dispersing in a PMMA matrix. Electrochemical and computational studies of complexes 4a and 4b revealed that the blue phosphorescence originates mainly from intraligand 3π → π* (3ILCT) transitions with relatively small 3MLCT mixing. A deep-blue OLED containing 4a as the light-emitting dopant was successfully fabricated using a solution-processed method, and the device exhibited blue photoluminescence with CIE coordinates of (0.17, 0.15) and a maximum external quantum efficiency (EQEmax) value of 6.2%. This article represents the pioneering study of a deep blue PhOLED using a Pt complex bearing a closo-monocarborane anion substituent, providing a new avenue into the preparation of novel triplet emitters based on boron-rich cluster anions.