Molecular design of luminescent Eu(III) complexes as lanthanide lasing material and their optical properties

Abstract Luminescent polymer (PMMA) containing a Eu(III) complex with a fast radiation rate and a high luminescence quantum efficiency (75 ± 5%), (bis-triphenylphosphineoxide)(tris-hexafluoroacetylacetonato)europium(III) (Eu(hfa) 3 (TPPO) 2 ), was fabricated. The quantum yield and the radiation rate of the luminescent polymer were found to be 75 ± 5% and 1.1 × 10 3  s −1 , respectively. An Eu(III) complex-doped polymer thin-film was also prepared by use of polyphenylsilsesquioxane (PPSQ) to construct a waveguide lanthanide laser. We propose a strategy for the molecular design of luminescent Eu(III) complexes aiming at lanthanide lasing.

[1]  Y. Wada,et al.  Enhanced Emission of Deuterated Tris(hexafluoroacetylacetonato)neodymium(III) Complex in Solution by Suppression of Radiationless Transition via Vibrational Excitation , 1996 .

[2]  H. Tamiaki,et al.  Specific recognition of chiral amino alcohols via lanthanide coordination chemistry: structural optimization of lanthanide tris(beta-diketonates) toward effective circular dichroism/fluorescence probing. , 2001, Inorganic chemistry.

[3]  J. Bünzli,et al.  Lanthanide Podates with Programmed Intermolecular Interactions: Luminescence Enhancement through Association with Cyclodextrins and Unusually Large Relaxivity of the Gadolinium Self-Aggregates , 2000 .

[4]  M. Fujimura,et al.  Quasi-phase-matched self-frequency-doubling waveguide laser in Nd:LiNbO/sub 3/ , 2000, IEEE Photonics Technology Letters.

[5]  W. Horrocks,et al.  Supramolecular coordination chemistry in aqueous solution: lanthanide ion-induced triple helix formation. , 2000, Inorganic chemistry.

[6]  M. Botta,et al.  Conjugates of cyclodextrins with charged and neutral macrocyclic europium, terbium and gadolinium complexes: sensitised luminescence and relaxometric investigations and an example of supramolecular relaxivity enhancement , 2000 .

[7]  Thorfinnur Gunnlaugsson,et al.  The Selectivity of Reversible Oxy-Anion Binding in Aqueous Solution at a Chiral Europium and Terbium Center: Signaling of Carbonate Chelation by Changes in the Form and Circular Polarization of Luminescence Emission , 2000 .

[8]  Yasuhiro Koike,et al.  Plastic optical fiber lasers and amplifiers containing lanthanide complexes. , 2002, Chemical reviews.

[9]  M L Lesiecki,et al.  Use of the thermal lens technique to measure the luminescent quantum yields of dyes in PMMA for luminescent solar concentrators. , 1982, Applied optics.

[10]  Y. Kai,et al.  Luminescent Polymer Containing the Eu(III) Complex Having Fast Radiation Rate and High Emission Quantum Efficiency , 2003 .

[11]  D. Reinhoudt,et al.  A Systematic Study of the Photophysical Processes in Polydentate Triphenylene-Functionalized Eu3+, Tb3+, Nd3+, Yb3+, and Er3+ Complexes , 2000 .

[12]  Tatsuhiko Yamanaka,et al.  Enhancement of luminescence of Nd3+ complexes with deuterated hexafluoroacetylacetonato ligands in organic solvent , 1996 .

[13]  T. Kitamura,et al.  Enhanced Luminescence of Lanthanide (III) Complexes in Polymer Matrices , 1999 .

[14]  Y. Wada,et al.  High Efficiency Near-IR Emission of Nd(III) Based on Low-Vibrational Environment in Cages of Nanosized Zeolites , 2000 .

[15]  Y. Wada,et al.  Novel Silicone Polymeric Material with High Thermal Stability for Optical Waveguides , 2002 .

[16]  Enzo Terreno,et al.  Lanthanide(III) chelates for NMR biomedical applications , 1998 .

[17]  S. Tomoda,et al.  The Structure of Diaquatris(1,1,1-trifluoro-2,4-pentanedionato)neodymium(III)–Acetone (1/1) , 1986 .

[18]  Keisuke Sasaki,et al.  Fabrication and superfluorescence of rare-earth chelate-doped graded index polymer optical fibers , 1997 .

[19]  A. Lempicki,et al.  ROOM‐TEMPERATURE OPERATION OF A EUROPIUM CHELATE LIQUID LASER , 1964 .

[20]  E. Würzberg,et al.  Energy gap law in the solvent isotope effect on radiationless transitions of rare earth ions , 1975 .

[21]  C. Su,et al.  Studies on lanthanide complexes of the tripodal ligand bis(2-benzimidazolylmethyl)(2-pyridylmethyl)amine. Crystal structures and luminescence properties , 2000 .

[22]  Joon Won Park,et al.  Luminescence spectroscopy of Eu(Bis-tris)3+ complexes in anhydrous DMF [Bis-tris = 2,2-bis(hydroxymethyl)-2,2′,2″-nitrilotriethanol]: luminescence quenching rate constants for the 5D0 state of Eu3+ by DMF and polyalcoholic OH groups , 2001 .

[23]  L. Chappell,et al.  Eu(III) macrocyclic complexes promote cleavage of and bind to models for the 5'-cap of mRNA. Effect of pendent group and a second metal ion. , 2000, Inorganic Chemistry.

[24]  Wada,et al.  Luminescence of Novel Neodymium Sulfonylaminate Complexes in Organic Media. , 2000, Angewandte Chemie.

[25]  Y. Wada,et al.  Low-vibrational luminescent polymers including tris(bis-perfluoromethane and ethanesulfonylaminate)neodymium(III) with 8 coordinated DMSO-d6 , 2003 .

[26]  J. Bünzli,et al.  Mono- and polymetallic lanthanide-containing functional assemblies: a field between tradition and novelty , 1999 .

[27]  J. Bünzli,et al.  Structural and photophysical properties of LnIII complexes with 2,2"-bipyridine-6,6"-dicarboxylic acid: surprising formation of a H-bonded network of bimetallic entities , 2000 .

[28]  R. Ziessel,et al.  Lanthanide tags for time-resolved luminescence microscopy displaying improved stability and optical properties. , 2001, Journal of the American Chemical Society.

[29]  R. Lauffer,et al.  Gadolinium(III) Chelates as MRI Contrast Agents: Structure, Dynamics, and Applications. , 1999, Chemical reviews.

[30]  E. Schimitschek,et al.  Organometallic Compounds as Possible Laser Materials , 1962, Nature.