Luminescent lanthanide mixed N-phthaloylglycinate and terephthalate coordination polymers: Structural and optical properties.

A new class of lanthanide mixed-carboxylate ligands compounds with formula {[Ln2 (phthgly)4 (bdc)(H2 O)6 ]·(H2 O)4 }∞ , labelled as Ln3+ : Eu (1) and Gd (2) coordination polymers (CP) were synthesized under mild reaction conditions between lanthanide nitrate salts and a solution of N-phthaloylglycine (phthgly) and terephthalic (bdc) ligands. The (1) and (2) coordination polymers were formed by symmetric binuclear units, in which phthgly and bdc carboxylate ligands are coordinated to the lanthanide ions by different coordination modes. Surprisingly, all organic ligands participate in hydrogen bonding interactions, forming an extremally rigid crystalline structure. The red narrow emission bands from the 5 D0 →7 FJ transitions of the Eu3+ ion show a high colour purity. The intramolecular energy transfer process from L→Eu3+ ion has been discussed. The experimental intensity parameters (Ω2,4 ) reflect lower angular distortion and polarizability of the chemical environment around the metal ion compared with other Eu3+ compounds reported in the literature. This novel class of coordination polymer offers a more attractive platform for developing luminescent functional materials for different applications.

Enhancing the Luminescence of Eu(III) Complexes with the Ruthenocene Organometallic Unit as Ancillary Ligand.

Five novel Eu(III)-ß-diketonate complexes containing ruthenocene ancillary ligands (1,1'-bis(diphenylphosphoryl)ruthenocene─RcBPO) were synthesized and characterized. The coordination compounds presented the general formula [Eu(ß-dik)3(RcBPO)], where ß-dik stands for 2-thenoyltrifluoroacetonate (tta), 3-benzoyl-1,1,1-trifluoroacetone (btf), 2-dibenzoylmethanate (dbm), 2-acetyl-1,3-indandionate (aind), and 2-benzoyl-1,3-indandionate (bind), and RcBPO stands for 1,1'-bis(diphenylphosphoryl)ruthenocene. The [Eu(aind)3(RcBPO)] complex crystallizes in a monoclinic Cc non-centrosymmetric space group with the europium site environment, assuming a bicapped trigonal prism coordination polyhedron with the symmetry point group close to C2v. Photoluminescent properties for the solid-state samples were described in terms of excitation, emission, lifetime decay curves, and intrinsic and overall quantum yields. The replacement of the two coordinated H2O molecules by the RcBPO ancillary ligand leads to great enhancements of the overall quantum yields (QEuL), with the minimum increment by a factor of 5 for the case of [Eu(btf)3(RcBPO)] and the maximum enhancement of 270 times for the case of the [Eu(dbm)3(RcBPO)] complex. In addition, theoretical calculations were carried out to model the spectroscopic properties of the investigated compounds. To obtain theoretical Judd-Ofelt parameters (Ωλ, λ = 2, 4, and 6) and intramolecular energy transfer rates, the JOYSpectra web platform was employed using the structure obtained from density functional theory calculations. Hence, a rate equation model provided theoretical overall quantum yields, which are in great agreement with measured data.

Luminescence properties of the Ln-EDTA complexes covalently linked to the chitosan biopolymers containing ß-diketonate as antenna ligands.

This paper reports on the preparation, characterization, and photoluminescence properties of novel hybrid materials, in which the EDTA-Ln-L complexes (where L: H2 O, acac, bzac, dbm, and tta ligands, and Ln: Eu, Gd, and Tb) were covalently linked to the precursor medium molecular weight chitosan surface (CS) matrices or on the chitosan surfaces previously crosslinked with epichlorohydrin (CSech). The emission spectra of these materials were characterized by intraconfigurational-4fN transitions centred on the Eu3+ and Tb3+ ions. Some broad bands from the polymeric matrix were also observed in the emission spectra, however the relative intensities of the intraconfigurational bands increased significantly for systems containing diketonate ligands when the antenna effect became more efficient. The values of the radiative rates (Arad ) were higher for crosslinked hybrid systems with epichlorohydrin, while nonradiative rates (Anrad ) presented the opposite behaviour. These data contributed to an increase in the values of emission quantum efficiency (η) for crosslinked materials. The effect of the modification process and antenna ligand on the values of intensities, intensity parameters Ω2 e Ω4 of the Eu3+ complexes were also investigated. The results showed that the crosslinked biopolymer surfaces have great potential for applications in molecular devices light converters.

Odd-Even Effect on Luminescence Properties of Europium Aliphatic Dicarboxylate Complexes.

The odd-even effect in luminescent [Eu2 (L)3 (H2 O)x ]⋅y(H2 O) complexes with aliphatic dicarboxylate ligands (L: OXA, MAL, SUC, GLU, ADP, PIM, SUB, AZL, SEB, UND, and DOD, where x=2-6 and y=0-4), prepared by the precipitation method, was observed for the first time in lanthanide compounds. The final dehydration temperatures of the Eu3+ complexes show a zigzag pattern as a function of the carbon chain length of the dicarboxylate ligands, leading to the so-called odd-even effect. The FTIR data confirm the ligand-metal coordination via the mixed mode of bridge-chelate coordination, except for the Eu3+ -oxalate complex. XRD results indicate that the highly crystalline materials belong to the monoclinic system. The odd-even effect on the 4 f-4 f luminescence intensity parameters (Ω2 and Ω4 ) is explained by using an extension of the dynamic coupling mechanism, herein named the ghost-atom model. In this method, the long-range polarizabilities ( α* ) were simulated by a ghost atom located at the middle of each ligand chain. The values of α* were estimated using the localized molecular orbital approach. The emission intrinsic quantum yield ( QLnLn ) of the Eu3+ complexes also presented an the odd-even effect, successfully explained in terms of the zigzag behavior shown by the Ω2 and Ω4 intensity parameters. Luminescence quenching due to water molecules in the first coordination sphere is also discussed and rationalized.

Red-green emitting and superparamagnetic nanomarkers containing Fe3O4 functionalized with calixarene and rare earth complexes.

The design of bifunctional magnetic luminescent nanomaterials containing Fe3O4 functionalized with rare earth ion complexes of calixarene and ß-diketonate ligands is reported. Their preparation is accessible through a facile one-pot method. These novel Fe3O4@calix-Eu(TTA) (TTA = thenoyltrifluoroacetonate) and Fe3O4@calix-Tb(ACAC) (ACAC = acetylacetonate) magnetic luminescent nanomaterials show interesting superparamagnetic and photonic properties. The magnetic properties (M-H and ZFC/FC measurements) at temperatures of 5 and 300 K were explored to investigate the extent of coating and the crystallinity effect on the saturation magnetization values and blocking temperatures. Even though magnetite is a strong luminescence quencher, the coating of the Fe3O4 nanoparticles with synthetically functionalized rare earth complexes has overcome this difficulty. The intramolecular energy transfer from the T1 excited triplet states of TTA and ACAC ligands to the emitting levels of Eu(3+) and Tb(3+) in the nanomaterials and emission efficiencies are presented and discussed, as well as the structural conclusions from the values of the 4f-4f intensity parameters in the case of the Eu(3+) ion. These novel nanomaterials may act as the emitting layer for the red and green light for magnetic light-converting molecular devices (MLCMDs).

Photoluminescence of europium(III) dithiocarbamate complexes: electronic structure, charge transfer and energy transfer.

For the first time, we observed photoluminescence in Eu(III) dithiocarbamate complexes at room temperature -- more specifically in [Eu(Et(2)NCS(2))(3)phen], [Eu(Et(2)NCS(2))(3)bpy] and the novel [Eu(Ph(2)NCS(2))(3)phen], where phen stands for 1,10-phenanthroline and bpy for 2,2'-bipyridine. Correlations between the electronic structure of the dithiocarbamate ligands on one hand, and covalency, intensity, and ligand field spectroscopic parameters on the other, could be established. Moreover, the relative values of the emission quantum efficiencies obtained for these complexes, as well as their dependence with temperature, could be satisfactorily described by a theoretical methodology recently developed.

Steady-state luminescence investigation of the binding of Eu(III) and Tb(III) ions with synthetic peptides derived from plant thionins.

This work reports Eu(III) and Tb(III) luminescence titrations in which the lanthanide ions were used as spectroscopic probes for Ca(II) ions to determine the metal binding ability of Ac-NESVKEEGGW-NH(2) and Ac-NESVKEDGGW-NH(2). These decapeptides correspond to the putative calcium binding region of the plant antifungal proteins SI-alpha1 from Sorghum bicolor and of Zeathionin from Zea mays, respectively. The luminescence spectra for the Eu(III)-decapeptide system (red emission) with the excitation at the Trp band at 280 nm showed an enhancement of the intensities of the 5D(0)-->7F(J) transitions (where J=0-4) with increments of Eu(III) ion concentration. The photoluminescence titration data of the terbium ion (green emission) in the decapeptide solutions showed intensification of the 5D(4)-->7F(J) transitions (J=0-6), similar to that observed for the Eu(III) ion. Thus, energy transfer from Ac-NESVKEEGGW-NH(2) and Ac-NESVKEDGGW-NH(2) to the trivalent lanthanide ions revealed that these peptides are capable of binding to these metal ions with association constants of the order of 10(5) M(-1). The amino acid derivative Ac-Trp-OEt also transferred energy to Tb(III) and Eu(III) ions as judged from the quenching of tryptophan luminescence. However, the energy transfers were significantly lower. Taken together the luminescence titration data indicated that Ac-NESVKEEGGW-NH(2) and Ac-NESVKEDGGW-NH(2) bind efficiently to both trivalent lanthanide ions and that these ions may be used as probes to distinguish an anionic peptide from a neutral amino acid derivative.

Synthesis and photophysical study of highly luminescent coordination compounds of rare earth ions with thenoyltrifluoroacetonate and AZT.

This work presents the study of the interaction between zidovudine (AZT) and rare earth (RE) ions with thenoyltrifluoroacetonate (TTA). The complexes [RE(TTA)(3) x (AZT)(2)] (where RE(III)=Eu and Gd) were prepared by reaction between the [RE(TTA)(3) x (H(2)O)(2)] precursors and AZT dissolved in acetone in the molar ratio 1:2. The obtained luminescent materials were characterized by microanalyses (C, H, N), complexometric titration, IR spectroscopy, X-ray powder diffraction and thermal analysis (DSC and TG/DTG). The luminescence data indicate that the substitution of the two water molecules by AZT in the europium complex causes an intensification of luminescence corresponding to the (5)D(0) -->(7)F(J) (J=0-4) transitions associated with one of the site symmetries. Based on the luminescence spectrum of the Eu(III)-compound the Omega(lambda) experimental intensity parameters (lambda=2 and 4) were calculated for the electronic transitions (5)D(0)-->(7)F(2, 4). The Omega(2) intensity parameter for this new compound is higher than for the precursor compound, suggesting an effective interaction between the AZT and the chemical environment of the Eu(III) ion. Luminescence data confirm that the AZT complex and precursor compound have a comparable emission quantum efficiency.