| 16749823 |
Matkovich KM, Thorne LM, Wolf MO, Pace TC, Bohne C, Patrick BO: Luminescence of ruthenium halide complexes containing a hemilabile phosphine pyrenyl ether ligand. Inorg Chem. 2006 Jun 12;45(12):4610-8.
A series of Ru (II) complexes, tcc-RuX2 (POC4Pyr-P,O) 2 (X = Cl (3), Br (4), I (5)), containing the hemilabile phosphine pyrenyl ether ligand 4-{2-(diphenylphosphino) phenoxy}butylpyrene (POC4Pyr (1)) are reported. The synthesis and spectroscopic properties of both the ligand, POC4pyr (1), and ligand oxide, P (=O) OC4pyr 2, and the solid-state structure of 1 are reported. Complexes 3-5 react rapidly with CO to give complexes ttt-RuX2 (CO) 2 (POC4pyr-P) 2 (X = Cl (6), Br (7), I (8)). No pyrene excimer emission is detected from 3-5; however, different intensities of excimer emission are observed for 6-8. The intensity of excimer emission decreases through the series, with 6 showing the most intense response. The emission is solely due to intramolecular pyrene excimers at low concentrations (< or =10 (-4) M). Comparison of the UV-vis and steady-state fluorescence spectra shows overlap between the low energy d-d absorption of 7 and 8 with excimer emission (480 nm), suggesting nonradiative energy transfer may be occurring. Once excess CO is removed, complexes 6-8 isomerize to cis-dicarbonyl complexes cct-RuX2 (CO) 2 (POC4Pyr-P) 2 (X = Cl (9), Br (10), I (11)). The intensity of excimer emission from 9-11 increases with respect to the excimer emission observed for 6-8, with 9 showing a significant increase in excimer intensity. |
1(0,0,0,1) |