Preparation of photoluminescent PMMA doped with tris(pyrazol-1-yl)borate lanthanide complexes (original) (raw)
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Thermal, Spectroscopy and Luminescent Characterization of Hybrid PMMA/Lanthanide Complex Materials
Materials, 2021
Novel hybrid materials based on the poly(methyl methacrylate) (PMMA) matrix and lanthanide(III) carboxylates Eu:2,6-DClB and Tb:2,6-DClB were synthesized and carefully analyzed in the context of their potential application in optically active polymer-based optical fibers. To determine the usefulness of the obtained materials, a careful thermal, mass spectroscopy, and optical characterization was performed, focusing on the features critical for the technology of optical fiber processing. In addition, the luminescent features of both lanthanide complexes and the resulting hybrid composites were carefully investigated to identify the processes responsible for light emission and to analyze the influence of the PMMA host on light emission intensity and spectral characteristics. The obtained results showed that both lanthanide carboxylate complexes exhibited intense luminescence in the red and green spectral range, typical of europium and terbium dopants, and that those features were well...
Synthesis, characterization and luminescence properties of Tb 3+ and Eu 3+-doped poly(acrylic acid
Materials Letters, 2003
A series of novel ternary rare earth complexes showing attractive luminescence properties were prepared with both neutral and anion ligands. Three azatriphenylene neutral ligands, 1,10-phenanthroline (phen), dipyrido [3,2-a: 2 ,3 -c] quinoxaline (dpq) and dipyrido [3,2-a: 2 ,3 -c] phenazine (dppz) were investigated systematically as sensitizers in the ternary rare earth complexes. Benzoate ions (BA − ) and phenoxyacetate ions (POA − ) were chosen as anion ligands. The compositions of these complexes were characterized by elemental analysis, rare earth coordination titration, molar conductivity measurement, IR spectroscopy, UV-vis absorption spectroscopy, 1 H NMR spectroscopy and TGA-DTA. The luminescence spectra, luminescence decay time and quantum efficiency of the complexes were also studied. The very strong luminescence intensities and rather long luminescence lifetimes (typically > 1.0 ms) were achieved for both Eu 3+ and Tb 3+ ternary complexes with phen and dpq as neutral ligands. Moreover, high quantum efficiencies (40-60%) were also obtained for Eu 3+ ternary complexes with phen and dpq as neutral ligands.
Indian Journal of Physics, 2012
Europium b-diketonate complexes Eu x Re (1-x) (TTA) 3 Phen, (Re = Y/Tb, TTA: thenoyl trifluro acetone, Phen: 1-10 Phenanthroline; x = 0.5) have been molecularly doped in poly methyl methacrylate matrix to study the concentration effect on the optical properties such as optical absorption and photoluminescence spectra for four different amounts of weight % (10, 25, 50 and 60 %). All these doped complexes show strong absorption peaks at 334 and 280 nm attributed to n-p* and p-p* transitions of b-diketonate ligand TTA respectively. The close absorptivity of all the complexes is due to the same tris chelated core TTA. Among the three complexes doped in PMMA matrix Eu 0.5 Tb 0.5 (TTA) 3 Phen complex shows hyper chromic shift with enhancement in the luminescent intensity. Enhancement of red light emission have been observed with the increase in wt% of all pure and doped systems in the order of Eu(TTA) 3 Phen, \ Eu 0.5 Y 0.5 (TTA) 3-Phen \ Eu 0.5 Tb 0.5 (TTA) 3 Phen. It has been observed that their PL intensity increases in the order of 10 [ 25 [ 50-60 %. However the luminescence intensity of these blended films with 50 and 60 % of rare earth complexes shows nearly equal value, indicating that the optimal doping concentration is about 50 % under the chosen experimental conditions. Hence these complexes are best suitable in fabricating eco-friendly organic light-emitting devices and displays by solution techniques, which can be operated at very low voltage.
Luminescent hybrid materials based on an europium organic complex and borate glasses
Journal of Non-Crystalline Solids, 2015
Hybrid materials (HM) were synthesized by high temperature reactions of inorganic glass matrices with an organometallic phosphor; B 2 O 3 and 80PbF 2-20B 2 O 3 were used as glassy matrices. The organometallic complex was tris(4,4,4-trifluoro-1-(2-naphthyl) butane-1,3-dionato-(1,10-phenanthroline) europium (III), (Eu(NTA) 3 (Phen)). The fabricated HMs were shaped as thin glassy plates. The PL spectra of HMs based on fused B 2 O 3 contained only the bands corresponding to Eu 3+ ion transitions and were similar to the spectra of the Eu(NTA) 3 (Phen) powder. For the HM made from an unfused B 2 O 3 , we observed the 503 nm PL band attributed to the ligand, but the Eu 3+ lines were more intense. The 80PbF 2-20B 2 O 3-based HM had a broad PL band (480 nm), which was more intense than the narrow Eu 3+ lines. To explain the obtained results, an exchange reaction that was accompanied by partial decomposition of the organic complex in the glass matrix was proposed. The Eu 3+ displacement in an oxidefluoride environment led to a decreased PL intensity to values that have typically been attributed to Eu 3+ doped inorganic glasses. Simultaneously, the ligands formed complexes with Pb, which resulted in an increased PL intensity.
Novel lanthanide complexes for visible and IR emission
Synthetic Metals, 2004
In this work we report the synthesis and photophysical properties of a novel ligand and its lanthanide complexes based on macrocycle 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid bearing 8-hydroxyquinoline as antenna. Visible and IR sensitized emission is obtained because of the efficient energy transfer from the antenna to the emitting ion. The interaction between ions and antenna is accounted for by suitable quantum chemical calculations. The good stability of the complexes and their solubility in organic solvents make them good candidates for the fabrication of plastic waveguides and optical amplifiers.
Molecules
This paper reports the synthesis, structure, photophysical, and optoelectronic properties of five eight-coordinate Europium(III) ternary complexes, namely, [Eu(hth)3(L)2], bearing 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedione (hth) as a sensitizer and L = H2O (1), dpso (diphenyl sulphoxide, 2), dpsoCH3 (4,4′-dimethyl diphenyl sulfoxide, 3), dpsoCl (bis(4-chlorophenyl)sulphoxide, 4), and tppo (triphenylphosphine oxide, 5) as co-ligands. The NMR and the crystal structure analysis confirmed the eight-coordinate structures of the complexes in solution and in a solid state. Upon UV-excitation on the absorption band of the β-diketonate ligand hth, all complexes showed the characteristic bright red luminescence of the Europium ion. The tppo derivative (5) displayed the highest quantum yield (up to 66%). As a result, an organic light-emitting device, OLED, was fabricated with a multi-layered structure—ITO/MoO3/mCP/SF3PO:[complex 5] (10%)/TPBi:[complex 5] (10%)/TmPyPB/LiF/Al—using ...
Luminescence of Ln3+ lanthanide complexes in polymer matrices
Polymer Science Series A, 2012
The photoluminescence properties of Tb 3+ and Eu 3+ complexes with polymer ligands containing various kinds of complexing groups-namely, carboxyl (5-20 mol %), pyridylquinoline (5 mol %), or pyridylnaphthyl (5 and 10 mol %) groups-in solution and block are considered. The chemical structure of a neutral comonomer (methyl methacrylate; styrene; isopropyl , phenyl , or benzylmethacrylamide; and N vinylamides) in polymer ligands is varied. The intensity of photoluminescence is dependent not only on the chemical nature of a complexing group but also the chemical nature of a neutral comonomer and a spacer. Variation in the nature of a comonomer and a ligand makes it possible to prepare complexes in which a high luminescence of a low molecular mass complex is preserved and advantages inherent in a polymer complex are acquired. The effect of the nature of the polymer matrix (photoactive and photoinert) on the efficiency of electronic excitation energy transfer is ascertained. The data on the photoluminescence of metal-polymer complexes that are based on polymer ligands containing vinylcarbozole units and that possess hole conduc tivity make it possible to regard them as materials for electroluminescence. The intensity of photolumines cence of these complexes is related to the competition of oppositely directed photophysical processes in a macromolecule: formation of excimers and migration of electronic excitation energy. An analysis of the pub lished data and of the results of the authors shows that detailed studies of these polymer systems in solution and in matrices are needed to gain insight into the relationship between photo and electroluminescence properties of metal-polymer complexes, because the matrix plays different roles in photoluminescence and electroluminescence (inner filter or conduction); as a consequence, the emission spectra may differ appre ciably. It is shown that the efficiency of electroluminescence may be improved if the transfer of energy from the lanthanide ligand in a complex to the conducting matrix is decreased.
Inorganic Chemistry, 2010
A novel efficient antenna complex of Eu 3þ [Eu(CPFHP) 3 (DDXPO)] supported by a highly fluorinated carbazolesubstituted β-diketonate ligand, namely, 1-(9H-carbazol-2-yl)-4,4,5,5,5-pentafluoro-3-hydroxypent-2-en-1-one (CPFHP) and the 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene oxide (DDXPO) ancillary ligand, has been synthesized, structurally characterized, and its photoluminescent behavior examined. The single-crystal X-ray diffraction analysis of Eu(CPFHP) 3 (DDXPO) revealed that this complex is mononuclear, and that the central Eu 3þ ion is surrounded by eight oxygen atoms, six of which are provided by the three bidentate β-diketonate ligands. The remaining two oxygen atoms are furnished by the chelating phosphine oxide ligand. The coordination polyhedron is best described as that of a distorted square antiprism. The photophysical properties of Eu(CPFHP) 3 (DDXPO) benefit from adequate protection of the metal by the ligands with respect to non-radiative deactivation as well as an efficient ligand-to-metal energy transfer process which exceeds 66% in chloroform solution with a quantum yield of 47%. As an integral part of this work, the synthesis, characterization, and luminescent properties of poly(methyl methacrylate) (PMMA) polymer films doped with Eu(CPFHP) 3 (DDXPO) are also reported. The luminescent efficiencies of the doped films (photoluminescence quantum yields 79-84%) are dramatically enhanced in comparison with that of the precursor complex. The new luminescent PMMA-doped Eu(CPFHP) 3 (DDXPO) complex therefore shows considerable promise for polymer light-emitting diode and active polymer optical fiber applications.
Journal of Analytical and Applied Pyrolysis, 2015
The complexes of lanthanide ions with V-shaped 4,4-sulfonyldibenzoic acid (H s sdb) of the formula Ln 2 sdb 3 •nH 2 O, where Ln = La(III), Nd(III), Eu(III), Tb(III), Dy(III), Yb(III) and n = 2-6 have been prepared by the hydrothermal method. The complexes were examined by elemental analysis, infrared spectroscopy (ATR-FTIR), X-ray diffraction pattern measurements and different methods of thermal analysis (TG-DSC and TG-FTIR). The luminescence properties of Eu(III) and Tb(III) complexes have been also investigated. The complexes crystallize in the triclinic (La, Nd and Eu) or monoclinic (Tb, Dy, Yb) crystal systems. Additionally, pentahydrate complexes of Dy(III) and Tb(III) are isostructural. 4,4-sulfonyldibenzoate ligand coordinates lanthanide ions through both carboxylate groups. Heating of the complexes resulted in dehydration and formation of stable Ln 2 sdb 3 compounds. Combustion of the organic ligand leads to the formation of intermediate stable lanthanide oxysulfate Ln 2 O 2 SO 4 which further decompose into the suitable oxides. In nitrogen atmosphere, investigated complexes release: water, carbon oxides, disulphur oxide and benzene molecules. The Eu(III) and Tb(III) complexes exhibit characteristic red and green luminescence.
Journal of Materials Science: Materials in Electronics
In this work, [Eu(tta) 3 (4-picNO) 2 ] and [Eu(dbm) 3 (4-picNO)] complexes were incorporated on different concentrations (x = 1, 3, 5, 10 and 15%) in PMMA polymeric matrix (4-picNO: 4-Methylpyridine N-oxide) by the solvent casting method, yielding transparent and highly luminescent polymeric films. These materials were analyzed by X-ray diffraction, scanning electron microscopy and by energy dispersive, ultraviolet-visible spectroscopy, luminescence and vacuum ultraviolet-ultraviolet spectroscopies. The luminescence spectra of doped PMMA films are in agreement with an efficient intramolecular diketonate (tta) ligand-to-europium energy transfer. Furthermore, the values of experimental intensity parameters (Ω 2,4) for luminescent polymeric materials were quite similar to those ones for isolated complexes, indicating that there is a homogeneous dispersion of Eu 3+ complexes in the polymeric matrix, preserving their chemical and structural features. These behavior were also observed from the CIE diagram that show great similarity between the (x,y) coordinates for the doped PMMA samples compared to the isolated β-diketonate complexes with a reddish color tuning. The photostability investigation of the doped PMMA polymeric films and Eu 3+ complexes has been also reported.