title: Brilliant photoluminescence and triboluminescence from ternary complexes of Dy(III) and Tb(III) with 3-phenyl-4-propanoyl-5-isoxazolonate and a bidentate phosphine oxide coligand.
abstract: Three new lanthanide heterocyclic β-diketonate complexes [Dy(PPI)3(EtOH)2] (1), [Dy(PPI)3(DPEPO)] (2), and [Tb(PPI)3(DPEPO)] (3) [where HPPI = 3-phenyl-4-propanoyl-5-isoxazolone and DPEPO = bis(2-(diphenylphosphino)phenyl)ether oxide] have been synthesized and fully characterized. Single-crystal X-ray diffraction analyses reveal that these complexes are mononuclear and that the central Ln(III) ion is coordinated to eight oxygen atoms that are provided by three bidentate β-diketonate ligands and ethanol or bidentate DPEPO in a distorted square antiprismatic geometry. These complexes have high molar absorption coefficients (up to 3 × 10(4) M(-1) cm(-1) at 285 nm) and display strong visible and, for Dy(III), NIR luminescence upon irradiation at the ligand-centered band in the range 250-350 nm. The emission quantum yields and the luminescence lifetimes at room temperature are 3 ± 0.5% and 15 ± 1 μs for 1, 12 ± 2% and 33 ± 1 μs for 2, and 42 ± 6% and 795 ± 1 μs for 3. Moreover, the crystals of 2 and 3 exhibit brilliant triboluminescence, visible in daylight.
authors.affiliation: Department of Advanced Materials Chemistry and WCU Center for Next Generation Photovoltaic Systems, Korea University, Jochiwon-eup, Sejong-si 339-700, Republic of Korea.
authors.forename: S
authors.initials: S
authors.lastname: Biju
authors.forename: N
authors.initials: N
authors.lastname: Gopakumar
authors.forename: J-C G
authors.initials: JC
authors.lastname: Bünzli
authors.forename: R
authors.initials: R
authors.lastname: Scopelliti
authors.forename: H K
authors.initials: HK
authors.lastname: Kim
authors.forename: M L P
authors.initials: ML
authors.lastname: Reddy
mesh_terms: D004419:Dysprosium / Q000737:chemistry*; D004735:Energy Transfer; D007555:Isoxazoles / Q000737:chemistry*; D008024:Ligands; D008163:Luminescent Measurements; D008958:Models, Molecular; D008968:Molecular Conformation; D055620:Optical Phenomena; D009942:Organometallic Compounds / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D013057:Spectrum Analysis; D013725:Terbium / Q000737:chemistry*
chemical_list: D007555:Isoxazoles; D008024:Ligands; D009942:Organometallic Compounds; D010720:Phosphines; D013725:Terbium; D004419:Dysprosium