title: Bis-cyclometalated Ir(III) complexes as efficient singlet oxygen sensitizers.
abstract: We report the singlet oxygen sensitization properties of a series of bis-cyclometalated Ir(III) complexes (i.e., (bt)2Ir(acac), (bsn)2Ir(acac), and (pq)2Ir(acac); bt = 2-phenylbenzothiazole, bsn = 2-(1-naphthyl)benzothiazole, pq = 2-phenylquinoline, and acac = acetylacetonate). Complexes with acetylacetonate ancillary ligands give singlet oxygen quantum yields near unity (PhiDelta = (0.7-1.0) +/- 0.1), whether exciting the ligand-based state or the lowest energy excited state (MLCT + 3LC). The singlet oxygen quenching rates for these beta-diketonate complexes were found to be small [(5 +/- 2) x 105 to (6 +/- 0.2) x 106 M-1 s-1], roughly 3 orders of magnitude slower than the corresponding phosphorescence quenching rate. Similar complexes were prepared with glycine or pyridine tethered to the Ir(III) center (i.e., (bsn)2Ir(gly) and (bt)2Ir(py)Cl; gly = glycine and py = pyridine). The glycine and pyridine derivatives give high singlet oxygen yields (PhiDelta = (0.7-1.0) +/- 0.1).
authors.affiliation: Department of Chemistry, California State University at Los Angeles, Los Angeles, CA 90032, USA.
authors.forename: Ruomei
authors.initials: R
authors.lastname: Gao
authors.forename: David G
authors.initials: DG
authors.lastname: Ho
authors.forename: Billy
authors.initials: B
authors.lastname: Hernandez
authors.forename: Matthias
authors.initials: M
authors.lastname: Selke
authors.forename: Drew
authors.initials: D
authors.lastname: Murphy
authors.forename: Peter I
authors.initials: PI
authors.lastname: Djurovich
authors.forename: Mark E
authors.initials: ME
authors.lastname: Thompson
mesh_terms: D007495:Iridium / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D017319:Photosensitizing Agents / Q000737:chemistry*; D026082:Singlet Oxygen / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D017319:Photosensitizing Agents; D026082:Singlet Oxygen; D007495:Iridium