A new tetrakis β-diketone ligand for NIR emitting LnIII ions: luminescent doped PMMA films and flexible resins for advanced photonic applications

A new antenna molecule containing four benzoyltrifluoroacetone (BTFA) moieties anchored to a single carbon atom and 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 homo- 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−1 cm−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 μs for SmIII and 2.6 ± 0.4% and 12.1 ± 0.1 μs 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.

[1]  S. Biju,et al.  Biphenylene-bridged mesostructured organosilica as a novel hybrid host material for LnIII (Ln = Eu, Gd, Tb, Er, Yb) ions in the presence of 2-thenoyltrifluoroacetone , 2013 .

[2]  P. B. Wyatt,et al.  Efficient sensitized emission in Yb(III) pentachlorotropolonate complexes. , 2013, Chemical communications.

[3]  B. Yan.  Recent progress in photofunctional lanthanide hybrid materials , 2012 .

[4]  Guangming Li,et al.  Highly luminescent bis-diketone lanthanide complexes with triple-stranded dinuclear structure. , 2012, Dalton transactions.

[5]  T. Kawai,et al.  Remarkable luminescence properties of lanthanide complexes with asymmetric dodecahedron structures. , 2011, Chemistry.

[6]  R. Tubino,et al.  Sensitized NIR erbium(III) emission in confined geometries: a new strategy for light emitters in telecom applications. , 2010, Journal of the American Chemical Society.

[7]  Koen Binnemans,et al.  Ionic liquid as plasticizer for europium(III)-doped luminescent poly(methyl methacrylate) films. , 2010, Physical chemistry chemical physics : PCCP.

[8]  Koen Binnemans,et al.  Lanthanide-based luminescent hybrid materials. , 2009, Chemical reviews.

[9]  S. Biju,et al.  3-Phenyl-4-acyl-5-isoxazolonate complex of Tb3+ doped into poly-β-hydroxybutyrate matrix as a promising light-conversion molecular device , 2009 .

[10]  J. Bünzli,et al.  Surprisingly bright near-infrared luminescence and short radiative lifetimes of ytterbium in hetero-binuclear Yb-Na chelates. , 2009, Inorganic chemistry.

[11]  C. K. Jayasankar,et al.  Dual emission from stoichiometrically mixed lanthanide complexes of 3-phenyl-4-benzoyl-5-isoxazolonate and 2,2′-bipyridine , 2009 .

[12]  Jean-Claude G Bünzli,et al.  Intrinsic quantum yields and radiative lifetimes of lanthanide tris(dipicolinates). , 2009, Physical chemistry chemical physics : PCCP.

[13]  J. Bünzli,et al.  Near-infrared luminescence of nine-coordinate neodymium complexes with benzimidazole-substituted 8-hydroxyquinolines. , 2008, Inorganic chemistry.

[14]  Lining Sun,et al.  Near-infrared emission from novel Tris(8-hydroxyquinolinate)lanthanide(III) complexes-functionalized mesoporous SBA-15. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[15]  S. Petoud,et al.  Azulene-moiety-based ligand for the efficient sensitization of four near-infrared luminescent lanthanide cations: Nd3+, Er3+, Tm3+, and Yb3+. , 2008, Chemistry.

[16]  Hwan-Kyu Kim,et al.  Ln(III)-cored complexes based on 2-thenoyltrifluoroacetone ligand for near infrared emission: Energy transfer pathway and transient absorption behavior , 2007 .

[17]  Biao Wang,et al.  Near-infrared luminescent lanthanide (Er, Nd) complexes covalently bonded to a terpyridine-functionalized silica matrix , 2007, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[18]  Lining Sun,et al.  Near-infrared luminescent mesoporous materials covalently bonded with ternary lanthanide Er(III), Nd(III), Yb(III), Sm(III), Pr(III) complexes , 2007 .

[19]  B. Kariuki,et al.  Synthesis, Crystal Structure, and Luminescent Properties of Novel Eu3+ Heterocyclic β-Diketonate Complexes with Bidentate Nitrogen Donors , 2006 .

[20]  S. T. Lee,et al.  Observation of near infrared and enhanced visible emissions from electroluminescent devices with organo samarium(III) complex , 2006 .

[21]  Lining Sun,et al.  Syntheses, Structures and Near‐IR Luminescent Studies on Ternary Lanthanide (ErIII, HoIII, YbIII, NdIII) Complexes Containing 4,4,5,5,6,6,6‐Heptafluoro‐1‐(2‐thienyl)hexane‐1,3‐dionate , 2006 .

[22]  Thorfinnur Gunnlaugsson,et al.  Soft Matter pH Sensing: From Luminescent Lanthanide pH Switches in Solution to Sensing in Hydrogels , 2006 .

[23]  Zhiyu Wang,et al.  Novel stoichiometrically erbium-ytterbium cocrystalline complex exhibiting enhanced near-infrared luminescence. , 2006, Inorganic chemistry.

[24]  Lining Sun,et al.  Covalent linking of near-infrared luminescent ternary lanthanide (Er(3+), Nd(3+), Yb(3+)) complexes on functionalized mesoporous MCM-41 and SBA-15. , 2006, The journal of physical chemistry. B.

[25]  J. Bünzli,et al.  Intense Near‐Infrared Luminescence of a Mesomorphic Ionic Liquid Doped with Lanthanide β‐Diketonate Ternary Complexes , 2005 .

[26]  Chen Xy,et al.  Analysis of Energy Level Structure and Excited-State Dynamics in a Sm3+ Complex with Soft-Donor Ligands: Sm(Et2Dtc)3(bipy) , 2005 .

[27]  S. Quici,et al.  Visible and near-infrared intense luminescence from water-soluble lanthanide [Tb(III), Eu(III), Sm(III), Dy(III), Pr(III), Ho(III), Yb(III), Nd(III), Er(III)] complexes. , 2005, Inorganic chemistry.

[28]  J. Klinowski,et al.  Photoluminescent layered lanthanide silicates. , 2004, Journal of the American Chemical Society.

[29]  M. Kotaki,et al.  A review on polymer nanofibers by electrospinning and their applications in nanocomposites , 2003 .

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

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

[32]  H. Güdel,et al.  High-resolution optical spectroscopy of Na(3)[Ln(dpa)(3)].13H(2)O with Ln = Er(3+), Tm(3+), Yb(3+). , 2002, Inorganic chemistry.

[33]  J. Moser,et al.  Visible and Near-Infrared Luminescence of Lanthanide-Containing Dimetallic Triple-Stranded Helicates: Energy Transfer Mechanisms in the SmIII and YbIII Molecular Edifices , 2002 .

[34]  M. Tsvirko,et al.  Determination of contributions of various molecular groups to nonradiative deactivation of electronic excitation energy in β-diketonate complexes of ytterbium(III) , 2001 .

[35]  H. Tanke,et al.  Detection of cell and tissue surface antigens using up-converting phosphors: a new reporter technology. , 1999, Analytical biochemistry.

[36]  Massimo Guardigli,et al.  Luminescent lanthanide complexes as photochemical supramolecular devices , 1993 .

[37]  Jean-Marie Lehn,et al.  Perspectives in Supramolecular Chemistry—From Molecular Recognition towards Molecular Information Processing and Self‐Organization , 1990 .

[38]  R. E. Whan,et al.  Intramolecular Energy Transfer in Rare Earth Chelates. Role of the Triplet State , 1961 .

[39]  S. Weissman,et al.  Intramolecular Energy Transfer The Fluorescence of Complexes of Europium , 1942 .