Luminescence of Ln3+ lanthanide complexes in polymer matrices (original) (raw)
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Chemistry & Chemical Technology
A monomer-2-methyl-5-phenylpentene-1dione-3,5, its solvent metal complex Eu(III)-water, hybrid metal complex Eu(III)-phenanthroline, new metallopolymers based on them are obtained. The results of above studies have shown that the configuration of the chelate unit is unchanged during polymerization. Using the electron microscopy the homogeneity of metal distribution in the polymer matrix of synthesized metallopolymer was confirmed. The similarity of monomers electronic absorption spectra with polymers spectra confirms the identical coordinative environment of lanthanide ions in both cases. The solubilization of europium β-diketonate complexes with phenanthroline was shown to change luminescence intensity in such complexes.
Luminescence of fusion materials of polymeric chain-structured lanthanide complexes
Polymer Journal, 2014
Polymeric chain-structured complexes were prepared with helical lanthanide complexes (LnL; Ln = Eu III , Tb III , Gd III) and benzene-dicarboxylate derivatives (benzene-1,4-dicarboxylate (bdc), 2-aminoterephtalate (atpa) and 2-hydoloxyterephtalate (htpa)), which show some noteworthy physicochemical properties, photoluminescence and thermal stabilities. The complex EuL-bdc shows bright luminescence originating from Eu III by UV excitation. The emission color can be tuned by mixing with TbL. The structures of these chain complexes were clarified with synchrotron X-ray powder diffraction measurements. The derivation of the linker moiety (bdc, atpa or htpa) was found to affect the intermetal energy transfer from Tb III to Eu III .
Luminescent Terbium Complexes with Polymer Ligands
Collection of Czechoslovak Chemical Communications, 2004
Alternating and statistical copolymers of 9-vinylcarbazole with diethyl fumarate (1), diethyl maleate (2), methacrylic acid (3), maleic anhydride (4), or maleic acid (5) were synthesized and characterized. These copolymers were tested as polymer ligands, that might be able to suppress the environmental vibronic quenching of a lanthanide ion and, simultaneously, to function as energy donors in the ligand-to-metal energy transfer processes. Time-resolved luminescence of a series of [Tb(III)-ligand] complexes in common and deuterated solvents revealed that the complexing properties of copolymers 3 or 5 are stronger than those of 1 or 2. Consequently, the strong binding affinity decreases the ligand-metal (donor-acceptor) distance and gives rise to an efficient ligand-to-metal energy transfer. Thus, the intensities of the long-lived emission (5D4→7F6, 5D4→7F5, 5D4→7F4, 5D4→7F3) of the [Tb(III)-3], [Tb(III)-5], and [Tb(III)-1] or [Tb(III)-2] complexes were found to be eight times, five t...
Dyes and Pigments, 2008
Tris(β-diketonato)europium(III) complexes of general formula [Eu(TPI) 3 ·L], with chelating ligands such as 3-phenyl-4-(4-toluoyl)-5-isoxazolone (HTPI) and adduct-forming reagents [L = H 2 O, tri-n-octylphosphane oxide (TOPO), triphenylphosphane oxide (TPhPO), 1,10-phenanthroline], have been synthesized and characterized by elemental analysis and FT-IR, 1 H NMR, and photoluminescence spectroscopy. The coordination geometries of the complexes were calculated using the Sparkle/AM1 (Sparkle model for the calculation of lanthanide complexes within the Austin model 1) model. The ligand-Eu 3+ energy-transfer rates were calculated using a model of intramolecular energy transfer in lanthanide coordination complexes reported in the literature. The room-temperature PL spectra of the europium(III) complexes are com-
Here, we have demonstrated a facile molecular approach to generate white light emission by combining carboxylic functionalized poly(m-phenylenevinylene)s polymeric architectures with lanthanide β-diketonate complexes. The new class of carboxylic functional conjugated polymeric materials was custom-designed from phenyl propanoic and acetic acids and structurally characterized by NMR, FT-IR, and MALDI-TOF spectroscopic techniques. The designed conjugated polymers were employed for the synthesis of lanthanide complexes in the presence of acetyl acetone (acac) as coligand and investigated their photophysical properties. For comparison, carboxylic-anchored oligo-phenylenevinylene (OPV) was also designed, characterized, and utilized for the synthesis of lanthanide complexes in the presence of acetyl acetone as coligand. Investigations revealed that carboxylic functionalized polymeric material with Eu3+-β-diketonate complex exhibits unique magenta emission when excited at 310 nm. On the other hand, carboxylic functionalized polymeric material with Tb3+-β-diketonate complex shows bright sky-blue emission. Interestingly, when Eu3+ and Tb3+ were incorporated into polymer backbone in equimolar ratio along with acetyl acetone as coligand, exhibited a white emission with CIE 1976 color coordinates x = 0.28, y = 0.34. The intrinsic quantum yield and lifetime of Ln3+ complexes have been evaluated. The singlet and triplet energy levels of the antenna chromophore ligands have been calculated and the probable energy transfer mechanisms in Ln3+ complexes have also been discussed. The effect of polymer structure and spacer effect on the photosensitizing of Tb3+ and Eu3+ ions was also investigated.
Lanthanide complexes of encapsulating ligands: Luminescent devices at the molecular level
Pure and Applied Chemistry, 1995
Lanthanide complexes of encapsulating ligands are studied as luminescent devices at the molecular level. The photophysical properties of the complexes which, up till now, showed the most intense luminescencepe reported. The luminescence intensity of these complexes is discussed,considering the efficiency of incident light-emitted light conversion, defined as the product of the absorption efficiency and the luminescence quantum yield. It is illustrated,how the metal luminescence intensity can be enhanced by adapting the ligands on basis of previously obtained experimental results. The possible application of these complexes in fluoroimmunoassays is examined.
Inorganica Chimica Acta, 2007
The two-component ligand systems 1 and 2 which contain 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) as the hosting unit for the lanthanide cations, and naphthalene (which is devoid of any chelating ability) or quinoline units, respectively, as chromophores, were synthesized. The 1:1 complexes with Gd 3+ , Eu 3+ and Tb 3+ have been studied in aqueous solution. Relaxometric properties for Gd AE 1 indicate that two water molecules (q = 2) are in the first coordination sphere of the metal ion whereas for Gd AE 2, q < 2 is found. For Gd AE 1, these results indicate that the naphthalene unit is not coordinated to the metal centre; for the case of quinoline, reasons for the lower hydration state are discussed. In case of Eu AE 1, Tb AE 1, Eu AE 2, and Tb AE 2 the absorption and luminescence spectra, the overall luminescence efficiencies, and the metal-centred lifetimes, were obtained both in water and deuterated water. The coordination features of these complexes were explored by comparing their luminescence properties, resulting in hydration state q = 2 and 1.4 for the cases of the complexes of 1 and 2, respectively. Use of the photophysical parameters in air-equilibrated water allowed the determination of the ligand-to-cation energy transfer efficiency, U EnT , leading to the overall emission sensitization process. For Eu AE 1, and Eu AE 2, we found U EnT = 0.034 and 0.078, respectively, supporting that also a non-coordinating chromophore like naphthalene, case of ligand 1, can transfer excitation energy to the metal centre.
Inorganic Chemistry, 2005
The synthesis of a new ligand (1) containing a single phenanthroline (phen) chromophore and a flexibly connected diethylenetriamine tetracarboxylic acid unit (DTTA) as a lanthanide (Ln) coordination site is reported [1 is 4-[(9methyl-1,10-phenantrol-2-yl)methyl]-1,4,7-triazaheptane-1,1,7,7-tetraacetic acid]. From 1, an extended series of watersoluble Ln‚1 complexes was obtained, where Ln is Eu(III), Tb(III), Gd(III), Sm(III), Dy(III), Pr(III), Ho(III), Yb(III), Nd(III), and Er(III). The stoichiometry for the association was found 1:1, with an association constant K A g 10 7 s -1 as determined by employing luminescence spectroscopy. The luminescence and photophysical properties of the series of lanthanide complexes were investigated in both H 2 O and D 2 O solutions. High efficiencies for the sensitized emission, φ se , in air-equilibrated water were observed for the Ln‚1 complexes of Eu(III) and Tb(III) in the visible region (φ se ) 0.24 and 0.15, respectively) and of Sm(III), Dy(III), Pr(III), Ho(III), Yb(III), Nd(III), and Er(III) in the vis and/or near-infrared region [φ se ) 2.5 × 10 -3 , 5 × 10 -4 , 3 × 10 -5 , 2 × 10 -5 , 2 × 10 -4 , 4 × 10 -5 , and (in D 2 O) 4 × 10 -5 , respectively]. For Eu‚1 and Tb‚1, luminescence data for water and deuterated water allowed us to estimate that no solvent molecules (q) are bound to the ion centers (q ) 0). Luminescence quenching by oxygen was investigated in selected cases.