2010302010183 ; 化學系 ; 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° 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 λmax 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.