Elaborate Design of Ag₈Au₁₀ Cluster [2]Catenane Phosphors for High-Efficiency Light-Emitting Devices

In this work, rational design of highly soluble and phosphorescent Ag-Au cluster complexes with exceptional [2]catenane structures is conducted using 1,8-diethynyl-9H-carbazole (H₃decz) as a rigid U-shaped ligand with a distinguished hole-transport character. The self-assembly reaction of H₃decz, Au⁺, and Ag⁺ generated phosphorescent Ag₄Au₆ cluster 1 (Φ_em = 0.22 in CH₂Cl₂) with H₂decz^- having a free ethynyl (-C≡CH) group. When the four free C≡CH groups in the Ag₄Au₆ complex 1 are further bound to four (PPh₃)Au⁺ and four (PPh₃)Ag⁺ moieties through M-acetylide linkages, the formation of Ag₈Au₁₀ cluster 2 not only eliminates nonradiative ethynyl C-H vibrational deactivation process but also improves dramatically the molecular rigidity so that the phosphorescent efficiency of the Ag₈Au₁₀ cluster 2 (Φ_em = 0.63) is nearly 3 times that of the Ag₄Au₆ cluster 1. The Ag₈Au₁₀ cluster structure is further rigidified using diphsophine Ph₂P(CH₂)₄PPh₂ (dppb) in place of PPh₃ so that the phosphorescence of the Ag₈Au₁₀ cluster 3 (Φ_em = 0.77) is more efficient than that of 2. Making use of the Ag₈Au₁₀ clusters as phosphorescent dopants, high-efficiency solution-processed organic light-emitting diodes (OLEDs) were achieved with current efficiency (CE) and external quantum efficiency (EQE) of 47.2 cd A^-1 and 15.7% for complex 2 and 50.5 cd A^-1 and 14.9% for complex 3.