Jean-Claude Bunzli - 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

Version 1

      Publication Details (including relevant citation   information):

      Biju,Silvanose, Gopakumar,N., B nzli,Jean-Claude G.,   Scopelliti,Rosario, Kim,Hwan Kyu, Reddy,M.L.P. Inorganic   Chemistry 2013 52 (15) 8750-8758

      Abstract: Three new lanthanide heterocyclic    -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 LnIII ion is coordinated to eight oxygen   atoms provided by three bidentate  -diketonate ligands and   ethanol or bidentate DPEPO in a distorted square antiprismatic   geometry. These complexes have high molar absorption coefficients   (up to 3 104 M-1cm-1 at 285 nm) and display strong visible and,   for DyIII, 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  s for 1, 12   2 % and 33   1  s for 2   and 42   6 % and 795   1 ms for 3. Moreover, the crystals of 2   and 3 exhibit brilliant triboluminescence, visible in   daylight.Three new lanthanide heterocyclic  -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 LnIII ion is coordinated to eight oxygen   atoms provided by three bidentate  -diketonate ligands and   ethanol or bidentate DPEPO in a distorted square antiprismatic   geometry. These complexes have high molar absorption coefficients   (up to 3 104 M-1cm-1 at 285 nm) and display strong visible and,   for DyIII, 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  s for 1, 12   2 % and 33   1  s for 2   and 42   6 % and 795   1 ms for 3. Moreover, the crystals of 2   and 3 exhibit brilliant triboluminescence, visible in daylight.

      Address (URL): http://dx.doi.org/10.1021/ic400913f