title: Synthesis and characterization of phosphorescent platinum and iridium complexes with cyclometalated corannulene.
abstract: Synthesis, structural and characterization data are provided for Pt(II) and Ir(III) complexes cyclometalated with 2-(corannulene)pyridine (corpy), (corpy)Pt(dpm) and (corpy)Ir(ppz)2 (dpm = dipivaloylmethanato, ppz = 1-phenylpyrazolyl). A third compound, (phenpy)Ir(ppz)2 (phenpy = 2-(5-phenanthryl)pyridyl), was also prepared to mimic the steric bulk of (corpy)Ir(ppz)2. X-ray analysis reveals bowl depths of 0.895 Å for (corpy)Pt(dpm) and 0.837 Å in (corpy)Ir(ppz)2. Neither complex displayed bowl-to-bowl stacking in the crystal lattice. A fluxional process for (corpy)Ir(ppz)2 attributed to bowl inversion of corrannulene is observed in solution with a barrier (ΔG(‡) = 13 kcal mol(-1)) and rate (k = 2.5 × 10(3) s(-1)) as determined using variable temperature (1)H NMR spectroscopy. All of the complexes display red phosphorescence at room temperature with quantum yields of 0.05 in solution and 0.2 in polymethyl methacrylate (PMMA).
authors.affiliation: Department of Chemistry, University of Southern California, Los Angeles, California 90089, USA. met@usc.edu.
authors.forename: John W
authors.initials: JW
authors.lastname: Facendola
authors.forename: Martin
authors.initials: M
authors.lastname: Seifrid
authors.forename: Jay
authors.initials: J
authors.lastname: Siegel
authors.forename: Peter I
authors.initials: PI
authors.lastname: Djurovich
authors.forename: Mark E
authors.initials: ME
authors.lastname: Thompson
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007495:Iridium / Q000737:chemistry*; D049408:Luminescent Agents / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D010984:Platinum / Q000737:chemistry*; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D049408:Luminescent Agents; D011084:Polycyclic Aromatic Hydrocarbons; C434863:corannulene; D007495:Iridium; D010984:Platinum