Jean-Claude Bunzli - A New Tetrakis �-Diketone Ligand for NIR Emitting Ln III  Ions: Luminescent Doped PMMA Films and Flexible Resins for Advanced Photonic Applications

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      Biju,Silvanose, Eom,Yu Kyung, B nzli,Jean-Claude G., Kim,Hwan Kyu   Journal of Materials Chemistry C 2013  1 (42) 6935-6944

      Abstract: A new antenna molecule containing four   benzoyltrifluoroacetone (BTFA) moieties anchored to a single   carbon atom connected through four flexible methoxy groups,   namely   1,1'-(4,4'-(2,2-bis((4-(4,4,4-trifluoro-3-oxobutanoyl)phenoxy)methyl)   propane-1,3-diyl)bis(oxy)bis   (4,1-phenylene))bis(4,4,4-trifluorobutane-1,3-dione) [H4L] has   been designed and synthesized. Using this ligand, a series of   **** and hetero metallic LnIII complexes of general formula   [LnL]NBu4 (where Ln = Sm (1), Gd (2), Er (3), Yb (4), Er0.5Yb0.5   (5), Er0.5Gd0.5 (6), Yb0.5Gd0.5 (7) and NBu4 = tetrabutyl   ammonium) have been isolated. All these complexes have high molar   absorption coefficients (> 40 000 M-1cm-1 around 330 nm in   DMF) and display strong visible (SmIII) and/or, NIR (SmIII,   ErIII, YbIII) luminescence in solid state and in DMF solution   upon irradiation at the ligand-centred bands in the range 250-400   nm. Furthermore, these complexes have been doped into PMMA   matrices yielding highly luminescent, photo-stable films and   flexible resins made of fibres with average diameter 300-400 nm.   Photoluminescence studies show that the newly designed ligand is   an adequate sensitizer for SmIII, YbIII and ErIII luminescence.   The emission quantum yields and the luminescence lifetimes at   room-temperature are 3.4   0.5 % and 79.1   1  s for SmIII and   2.6   0.4 % and 12.1   0.1  s for YbIII in solid state.   Furthermore the overall quantum yields and lifetime measurements   for the mixed metallic complex show that YbIII -ErIII energy   transfer occurs resulting in enhanced ErIII emission

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