title: Neutral Ru(II)-based emitting materials: a prototypical study on factors governing radiationless transition in phosphorescent metal complexes.
abstract: In addition to the metal-centered dd transition that is widely accepted as a dominant radiationless decay channel, other factors may also play important roles in governing the loss of phosphorescence efficiency for heavy-transition-metal complexes. To conduct our investigation, we synthesized two dicarbonylruthenium complexes with formulas [Ru(CO)2(BQ)2] (1) and [Ru(CO)2(DBQ)2] (2), for which the cyclometalated ligands BQ and DBQ denote benzo[h]quinoline and dibenzo[f,h]quinoxaline, respectively. Replacing one CO ligand with a P donor ligand such as PPh2Me and PPhMe2 caused one cyclometalated ligand to undergo a 180 degrees rotation around the central metal atom, giving highly luminous metal complexes [Ru(CO)L(BQ)2] and [Ru(CO)L(DBQ)2], where L = PPh2Me and PPhMe2 (3-6), with emission peaks lambda(max) in the range of 571-656 nm measured in the fluid state at room temperature. It is notable that the S0-T1 energy gap for both 1 and 2 is much higher than that of 3-6, but the corresponding phosphorescent spectral intensity is much weaker. Using these cyclometalated Ru metal complexes as a prototype, our experimental results and theoretical analysis draw attention to the fact that, for complexes 1 and 2, the weaker spin-orbit coupling present within these molecules reduces the T1-S0 interaction, from which the thermally activated radiationless deactivation may take place. This, in combination with the much smaller 3MLCT contribution than that observed in 3-6, rationalizes the lack of room-temperature emission for complexes 1 and 2.
authors.affiliation: Department of Chemistry and Instrumentation Center, National Taiwan University, Taipei 106, Taiwan.
authors.forename: Elise Y
authors.initials: EY
authors.lastname: Li
authors.forename: Yi-Ming
authors.initials: YM
authors.lastname: Cheng
authors.forename: Cheng-Chih
authors.initials: CC
authors.lastname: Hsu
authors.forename: Pi-Tai
authors.initials: PT
authors.lastname: Chou
authors.forename: Gene-Hsiang
authors.initials: GH
authors.lastname: Lee
authors.forename: I-Hui
authors.initials: IH
authors.lastname: Lin
authors.forename: Yun
authors.initials: Y
authors.lastname: Chi
authors.forename: Chao-Shiuan
authors.initials: CS
authors.lastname: Liu