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ABSTRACT: The synthesis of a new linear bis-tetraamine ligand , based on two 1,4,8,11-tetraazaundecane units grafted at the 2 and 6 positions of a pyridinyl linker substituted by an anthracenyl fluorophore in the para position, is described and anion complexation studies of with anionic substrates are reported. The protonation pattern and the study of the binding properties of in an aqueous medium with two anionic substrates, the nucleotide adenosine triphosphate () and the herbicide glyphosate (N-(phosphonomethyl)glycine, ), were investigated by means of potentiometry, NMR spectroscopy and absorption and emission spectroscopic techniques. To decipher the impact of the chromophoric linker on the complexation process and to highlight its optical properties, a comparison is established with its previously reported analog devoid of the anthracenyl group. The results unambiguously show that the protonation and complexation properties are preserved despite the presence of the bulky linker, allowing for the use of as a fluorescent sensor for and .
Dalton Transactions 01/2013; · 3.84 Impact Factor
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ABSTRACT: Homodinuclear lanthanide complexes derived from a ligand featuring two DO3A chelating sites linked by a 4,4'-dimethyl-2,2'-bipyridyl spacer were prepared and characterized. The bipyridyl coordination site of was used to introduce Ru(Bpy)(2) and Re(CO)(3)Cl moieties, leading to the formation of heterometallic d-f(2) complexes with general formulae [Ln(2)··Ru(Bpy)(2)](2+) (Ln = Nd, Eu, Tb, Yb and Lu) and [Ln(2)··Re(CO)(3)Cl] (Ln = Nd, Yb and Lu). The luminescence properties of the complexes were investigated by means of absorption spectroscopy and steady-state and time-resolved luminescence spectroscopy covering the visible and NIR regions. Both Ru and Re chromophores were shown to act as efficient sensitizers of the NIR emission of Yb and Nd in aqueous solutions. We also consider the unsaturated coordination spheres of the Ln cations in the Ln(2)· complexes, which form ternary complexes with bidentate anions without showing particular synergistic effects for polyanionic species.
Dalton Transactions 01/2013; · 3.84 Impact Factor
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ABSTRACT: Four new dicyanamide (dca) bridged multinuclear Zn(II)-Schiff-base complexes, {[Zn(2)L(1)(μ(1,5)-dca)dca]·CH(3)OH}(2) (1), [Zn(2)L(2)(μ(1,5)-dca)dca](n) (2), [Zn(3)L(3)(2)(μ(1,5)-dca)(2)](n) (3), and [(ZnL(4))(2)Zn(μ(1,5)-dca)dca](n) (4), have been synthesized using four different Schiff bases L(1)H(2) = N,N(/)-bis(3-methoxysalicylidenimino)-1,3-diaminopentane, L(2)H(2) = N,N'-bis(5-bromo-3-methoxysalicylidenimino)-1,3-diaminopropane, L(3)H(2) = N,N'-bis(5-bromosalicylidenimino)-1,3-diaminopropane, and L(4)H(2) = N,N'-bis(5-chlorosalicylidenimino)-1,3-diaminopropane and NaN(CN)(2) in order to extend the metal-ligand assembly. The directional properties of linear end-to-end bridging dca ligands have resulted in different metal ion connectivities leading to unique variety of templates in each of the complexes. All the ligands and complexes have been characterized by microanalytical and spectroscopic techniques. The structures of the complexes have been conclusively determined by single crystal X-ray diffraction studies. Thermogravimetric analyses have been performed to investigate the thermal stability of the metal-organic frameworks. Finally, the photoluminescence properties of the complexes as well as their respective ligands have been investigated with a comparative approach.
Inorganic Chemistry 10/2012; · 4.60 Impact Factor
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ABSTRACT: Ligand L, based on two do3a moieties linked by the methylene groups of 6,6'-dimethyl-2,2'-bipyridine, was synthesized and characterized. The addition of Ln salts to an aqueous solution of L (0.01 M Tris-HCl, pH 7.4) led to the successive formation of [LnL] and [Ln(2)L] complexes, as evidenced by UV/Vis and fluorescence titration experiments. Homodinuclear [Ln(2)L] complexes (Ln = Eu, Gd, Tb, Yb, and Lu) were prepared and characterized. The (1)H and (13)C NMR spectra of the Lu and Yb complexes in D(2)O solution (pD = 7.0) showed C(1) symmetry of these species in solution, pointing to two different chemical environments for the two lanthanide cations. The analysis of the chemical shifts of the Yb complex indicated that the two coordination sites present square antiprismatic (SAP) coordination environments around the metal ions. The spectroscopic properties of the [Tb(2)L] complex upon ligand excitation revealed conventional behavior with τ(H2O) = 2.05(1) ms and ϕ(H2O) = 51%, except for the calculation of the hydration number obtained from the luminescent lifetimes in H(2)O and D(2)O, which pointed to a non-integer value of 0.6 water molecules per Tb(III) ion. In contrast, the Eu complex revealed surprising features such as: 1) the presence of two and up to five components in the (5)D(0)→(7)F(0) and (5)D(0)→(7)F(1) emission bands, respectively; 2) marked differences between the normalized spectra obtained in H(2)O and D(2)O solutions; and 3) unconventional temporal evolution of the luminescence intensity at certain wavelengths, the intensity profile first displaying a rising step before the occurrence of the expected decay. Additional spectroscopic experiments performed on [Gd(2-x)Eu(x)L] complexes (x = 0.1 and 1.9) confirmed the presence of two distinct Eu sites with hydration numbers of 0 (site I) and 2 (site II), and showed that the unconventional temporal evolution of the emission intensity is the result of an unprecedented intramolecular Eu-to-Eu energy-transfer process. A mathematical model was developed to interpret the experimental data, leading to energy-transfer rates of 0.98 ms(-1) for the transfer from the site with q=0 to that with q=2 and vice versa. Hartree-Fock (HF) and density functional theory (DFT) calculations performed at the B3LYP level were used to investigate the conformation of the complex in solution, and to estimate the intermetallic distance, which provided Förster radii (R(0)) values of 8.1 Å for the energy transfer from site I to site II, and 6.8 Å for the reverse energy transfer. These results represent the first evidence of an intramolecular energy-transfer equilibrium between two identical lanthanide cations within a discrete molecular complex in solution.
Chemistry 05/2012; 18(26):8163-73. · 5.93 Impact Factor
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ABSTRACT: A Gd complex based on a polyphosphonated pyridyl ligand shows a very high stability in aqueous solution (log K(EuL) = 25.7), a high relaxivity (8.5 mM(-1) s(-1) at 25 °C and 20 MHz) and a marked and selective relaxivity enhancement (37%) in the presence of Mg(2+), opening interesting perspectives for the design of cation responsive contrast agents.
Chemical Communications 03/2012; 48(34):4085-7. · 6.17 Impact Factor
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ABSTRACT: The syntheses of a new cyclen-based ligand L(2) containing four N-[2-(2-hydroxyethoxy)ethyl]acetamide pendant arms and of its lanthanide(III) complexes [LnL(2)(H(2)O)]Cl(3) (Ln = La, Eu, Tb, Yb, or Lu) are reported, together with a comparison with some Ln(III) complexes of a previously reported analogue L(1) in which two opposite amide arms have been replaced by coordinating pyridyl units. The structure and dynamics of the La(III), Lu(III), and Yb(III) complexes in solution were studied by using multinuclear NMR investigations and density functional theory calculations. Luminescence lifetime measurements in H(2)O and D(2)O solutions of the [Ln(L(2))(H(2)O)](3+) complexes (Ln = Eu or Tb) were used to investigate the number of H(2)O molecules coordinated to the metal ion, pointing to the presence of an inner-sphere H(2)O molecule in a buffered aqueous solution. Fluoride binding to the latter complexes was investigated using a combination of absorption spectroscopy and steady-state and time-resolved luminescence spectroscopy, pointing to a surprisingly weak interaction in the case of L(2) (log K = 1.4 ± 0.1). In contrast to the results in solution, the X-ray crystal structure of the lanthanide complex showed the ninth coordination position occupied by a chloride anion. In the case of L(1), the X-ray structure of the [(EuL(1))(2)F] complex features a bridging fluoride donor with an uncommon linear Eu-F-Eu entity connecting two almost identical [Eu(L(1))](3+) units. Encapsulation of the F(-) anion within the two complexes is assisted by π-π stacking between the pyridyl rings of two complexes and C-H···F hydrogen-bonding interactions involving the anion and the pyridyl units.
Inorganic Chemistry 11/2011; 50(24):12508-21. · 4.60 Impact Factor
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ABSTRACT: A synthetic approach is developed to obtain families of luminescent lanthanide complexes and markers from a generic family of precursors built from nonadentate coordination sites. The syntheses of the precursors, based on a directed regioselective nucleophilic aromatic substitution on polyfluoropyridines, are described. Functionalisation of the synthons on the aromatic moieties allowed the introduction of labelling functions and/or the extension of the electronic delocalisation, with concomitant changes in the spectroscopic properties. The synthesis of two such families of ligands and of some of their complexes of Eu(III) and Tb(III) are described, and the photo-physical properties of the complexes were measured, revealing excellent luminescence quantum yields reaching unity in some cases. For some of these complexes, the emphasis was further put on the preparation of an N-hydroxylsuccinimide (NHS) ester as activated function for labelling. The Tb and La complexes in the NHS activated form were synthesized and fully characterized. The labelling was first demonstrated on amino functionalized polymer beads and characterized by time-resolved luminescence microscopy. In a second step, the activated Tb complex was used for the labelling of GFR44 monoclonal antibody, and was applied to the detection of carcinoembryonic antigene (CEA) within the frame of a time-resolved fluoroimmunoassay. Comparison with a commercially available kit based on a europium cryptate as energy donor confirms the efficiency of Tb to act as an energy donor with an unoptimised 35% increase of the detection efficiency.
Chemistry 07/2011; 17(33):9164-79. · 5.93 Impact Factor
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ABSTRACT: In this contribution we present two ligands based on a do3a platform containing a picolinate group attached to the fourth nitrogen atom of the cyclen unit, which are designed for stable lanthanide complexation in aqueous solutions. Potentiometric measurements reveal that the thermodynamic stability of the complexes is very high (log K = 21.2-23.5), being comparable to that of the dota analogues. Luminescence lifetime measurements performed on solutions of the Eu(III) and Tb(III) complexes indicate that the complexes are nine coordinate with no inner-sphere water molecules. A combination of density functional theory (DFT) calculations and NMR measurements shows that for the complexes of the heaviest lanthanides there is a major isomer in solution consisting of the enantiomeric pair Λ(δδδδ) and Δ(λλλλ), which provides square antiprismatic coordination (SAP) around the metal ion. Analysis of the Yb(III)-induced paramagnetic shifts unambiguously confirms that these complexes have SAP coordination in aqueous solution. For the light lanthanide ions however both the SAP and twisted-square antiprismatic (TSAP) isomers are present in solution. Inversion of the cyclen ring appears to be the rate-determining step for the Λ(δδδδ) ↔ Δ(λλλλ) enantiomerization process observed in the Lu(III) complexes. The energy barriers obtained from NMR measurements for this dynamic process are in excellent agreement with those predicted by DFT calculations. The energy barriers calculated for the arm-rotation process are considerably lower than those obtained for the ring-inversion path. Kinetic studies show that replacement of an acetate arm of dota by a picolinate pendant results in a 3-fold increase in the formation rate of the corresponding Eu(III) complexes and a significant increase of the rates of acid-catalyzed dissociation of the complexes. However, these rates are 1-2 orders of magnitude lower than those of do3a analogues, which shows that the complexes reported herein are remarkably inert with respect to metal ion dissociation.
Inorganic Chemistry 04/2011; 50(9):4125-41. · 4.60 Impact Factor
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ABSTRACT: The synthesis of ligand L(P)H(8), based on a 2,6-bispyrazolyl-pyridine scaffold functionalized by iminobismethylenephosphonate functions, is described and its pK values were determined by a combination of pH-spectrophotometric titrations and potentiometry. The interaction of L(P) with Tb(3+) was investigated in water (0.01 M TRIS/HCl pH = 7.0) by means of UV-vis and fluorescence titration experiments and evidenced the formation of at least three species with 1:1; 1:2, and 2:1 M-L ratios, the 1:1 complex appearing as particularly stable under these conditions (log K(cond) > 8). Na(4)[LnL(P)H] complexes (Ln = Eu and Tb) were prepared and characterized by elemental analysis, IR spectroscopy, and electrospray mass spectrometry. Their photophysical properties were investigated in aqueous solutions, revealing an excellent shielding of the Ln cations from the solvent environment (no water molecules in the first coordination sphere), very long luminescence lifetimes (τ(H(2)(O)) = 1.50 and 3.28 ms, respectively, for Eu and Tb) and reasonable luminescent quantum yields (ϕ(H(2)(O)) = 2.4 and 37%, respectively, for Eu and Tb). Using fetal bovine serum as a model for biological media showed the Tb complex to remain luminescent in these conditions. The structure of the europium complex was studied by means of density functional theory (DFT) modeling, confirming the wrapping of the ligand around the cation, and the very good shielding of the coordinated Ln cation. The conditional stability constant for the formation of the Tb complex with L(P) was determined by competition experiments with EDTA and monitored by fluorescence spectroscopy (log K(TbL(P)cond) = 14.1 ± 0.3, 0.01 M TRIS/HCl, pH = 7.4) and was used to determine the thermodynamic constant (log K(TbL(P)) = 20.4 ± 0.4). A systematic comparison with ligand L(C), in which phosphonate functions are replaced by carboxylate ones, is made throughout the study, highlighting the large interest of the introduction of phosphonate moieties to obtain biologically stable luminescent lanthanide complexes.
Inorganic Chemistry 01/2011; 50(5):1689-97. · 4.60 Impact Factor
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ABSTRACT: The synthesis of ligand L based on a 2,6-bis[(N,N-bis(methylene phosphonic acid)aminomethyl] pyridine scaffold is described. Potentiometry combined with UV-Vis absorption spectrophotometric titrations were used to determine the protonation constants of the ligand and the stability constants of its corresponding Cu(II), Ni(II), Zn(II) and Ga(III) cations (0.1 M NaClO(4), 25.0 °C). The physico-chemical approach revealed very large stability constants for Cu(II) complexation (logK(CuL) = 22.71(7)) reflected in a very high pCu(II) value of ∼ 15.5 (pH = 7.4, [L](tot) = 10(-5) M, [Cu](tot) = 10(-6) M), close to those measured for the strong methylphosphonate functionalized cyclen chelators. Based on a literature survey, a correlation is proposed between the pK values of branched polyamine ligands and their stability constants for Cu(II) complexation, allowing for an estimation of the latter on the basis of the protonation constants of L. Ligand L was also shown to be very selective towards Cu(II) compared to the other cations studied (ΔlogK > 4). UV-Vis spectroscopy and kinetic measurements indicated that the formation of the cupric complexes with L is very fast, which, in combination with all other properties, makes it an excellent non-cyclic target for Cu(II) radiopharmaceutical within the frame of (64)Cu positron emission tomography imaging and radiotherapy.
Dalton Transactions 10/2010; 39(38):9055-62. · 3.84 Impact Factor
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Angewandte Chemie International Edition 02/2010; 49(8):1396-401. · 13.45 Impact Factor
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Joy Chakraborty,
Aurkie Ray,
Guillaume Pilet,
Guillaume Chastanet,
Dominique Luneau,
Raymond F Ziessel, Loïc J Charbonnière,
Luca Carrella,
Eva Rentschler,
M S El Fallah,
Samiran Mitra
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ABSTRACT: A novel family of homodinuclear complexes of the general formula [Ln(2)L(2)(X)(2)] (where Ln = Nd(3+), Pr(3+), Sm(3+) and Tb(3+) for 1, 2, 3 and 4, respectively and X, the coordinated NO(3)(-) or Cl(-) anion) has been synthesised from the corresponding lanthanide(III) salts with the pentadentate dianionic Schiff base ligand, H(2)L [N(1),N(3)-bis(salicylideneimino)diethylenetriamine], that exhibits a N(3)O(2) donor set. Single crystal X-ray diffraction studies evidenced the isostructurality of this family of centrosymmetric neutral dinuclear entities where the Ln(III) metal centres are coupled together by two phenolato oxygen atoms belonging to two units of ligand (H(2)L). Interestingly, the two other phenolato groups of H(2)L are mono-coordinated to the metal ions. Temperature dependence (2-300K) magnetic susceptibility studies suggest the presence of an antiferromagnetic interaction operating via double phenolato bridges. Photoluminescence activities of the complexes have been studied and compared with their precursor ligand. All the complexes have been characterised with microanalytical and several spectroscopic techniques.
Dalton Transactions 12/2009; · 3.84 Impact Factor
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ABSTRACT: The synthesis of ligand L(1), based on the tetramethyl ester of [4'-ethynyl-(6,6''-bis(aminomethyl))-2,2':6',2''-terpyridine]tetrakisacetate, and its acidic form L(2), are described. Using a Cu-assisted coupling reaction, L(1) was connected to the Pt atom of a [(tpy)Pt] precursor (tpy = 2,2':6',2''-terpyridine) to afford the [(tpy)PtL(1)](BF(4)) metallosynthon, from which a hydrolysis reaction gave Na(3)[(tpy)PtL(2)]. The photophysical properties of the metallosynthons were studied by means of absorption and steady state emission spectroscopic techniques in various solvents, which revealed a dramatic impact of the solvent polarity. DFT and TDDFT calculations (B3LYP) were used to investigate the absorption and emission properties of the [(tpy)PtL(1)](+) system both in vacuo and in different solvents. Spectrophotometric titrations of [(tpy)PtL(1)](+) with EuCl(3) x 6 H(2)O in acetonitrile revealed the formation of complicated mixtures of complexes with different [(tpyPt(1))(x)Eu(y)] stoichiometries, all of which display the typical Eu(III) centred luminescence upon excitation into the Pt centred (1)MLCT absorption band. The energy transfer from the Pt subunit of [(tpy)PtL(2)](3-) to Eu(III) is inefficient in polar solvents, but it is restored in a TFA-CH(2)Cl(2) mixture, together with the observation of a new emission band at 684 nm, likely arising from a charge transfer process involving reduction of Eu(III).
Dalton Transactions 08/2009; · 3.84 Impact Factor
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Berichte der deutschen chemischen Gesellschaft 06/2009; 2009(26):3993 - 4000. · 2.94 Impact Factor
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ABSTRACT: Using a regioselective strategy for nucleophilic aromatic substitution on polyfluoropyridines, a nonacoordinating precursor was designed that is adequately suited for complexation of lanthanide cations. Further functionalizations afforded numerous applications for near-IR emission, two-photon absorption spectroscopy, or the formation of luminescent gels.
Inorganic Chemistry 05/2009; 48(11):4601-3. · 4.60 Impact Factor
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Berichte der deutschen chemischen Gesellschaft 06/2008; 2008(21):3241 - 3251. · 2.94 Impact Factor
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Berichte der deutschen chemischen Gesellschaft 05/2008; 2008(18):2856 - 2862. · 2.94 Impact Factor
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ABSTRACT: Turnip yellow mosaic virus (TYMV) is an icosahedral plant virus with an average diameter of 28 nm and can be isolated in gram quantities from turnip or Chinese cabbage inexpensively. In this study, it was selected as a prototype bionanoparticle for time-resolved fluoroimmuno assay (TRFIA). Two types of reactive amino acid residues were employed to anchor luminescent terbium complexes and biotin groups based on orthogonal chemical reactions. While terbium complexes were used as luminescent signaling groups, biotin motifs acted as a model ligand for protein binding. The bioconjugation results were confirmed by MS and Western blot analysis. Steady-state and time-resolved luminescence study of the dual-modified viruses demonstrated that the spectroscopic properties of the Tb complex are unperturbed by the labeling procedure. The dual-modified particle was probed by fluorescence resonance energy transfer (FRET) experiments using avidin labeled with an Alexa488 fluorophore, which bound to the biotin on the surface of the particle, as an energy acceptor, and terbium complexes as an energy donor. The emission and excitation spectra of the dual-labeled TYMV particle displayed residual virus fluorescence and Tb luminescence upon ligand-centered excitation. The Tb luminescence lifetime was 1.62 ms and could be effectively fitted with a single-exponential behavior. In the TRFIA, an efficient transfer of 66% was observed, and the calculation using the Förster radius of 41 A allowed for an estimation of the average donor-acceptor distance of 36 A. Our studies show that the two reactive sites can communicate with each other on the surface of a nanoscale biological assembly. In particular, the ligand-receptor binding (biotin and avidin in this paper) was not interfered with when anchored to the surface of TYMV. Therefore, as a prototype of polyvalent bionanoparticles, TYMV can be used as scaffold for sensor development with TRFIA.
Journal of the American Chemical Society 07/2007; 129(25):7799-806. · 9.91 Impact Factor
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ABSTRACT: The synthesis of ligand H3 based on a disymmetrically substituted terpyridine core functionalised by a carboxylic acid in the 6-position and a bis(carboxymethyl)aminomethyl function in the 6''-position is described. The coordination behaviour of this heptadentate (4N/3O) ligand with lanthanide cations (Ln=Eu, Gd and Tb) was studied in solution showing the formation of complexes with [Ln] stoichiometry. Complexes with general formula [Ln(H2O)2] were isolated from neutral water solutions containing equimolar amounts of cations and ligands, and the complexes were characterized in the solid state (elemental analysis, IR) and in solution (mass spectrometry). The photo-physical properties of the luminescent complexes of Eu and Tb were studied in water solution by means of absorption, steady state and time-resolved emission spectroscopies. Evolution of the luminescence lifetimes of the Eu and Tb complexes in H2O and D2O reveals the presence of two water molecules coordinated in the first coordination sphere of the cations. Despite this important hydration number, the overall luminescence quantum yields of the complexes remained elevated, especially in the case of Tb (Phi=22.0 and 6.5% respectively for Tb and Eu). Upon crystallisation the Gd complex formed dimeric species in which two gadolinium atoms are each heptacoordinated by one ligand, the coordination sphere being completed by a single water molecule and a bridging carboxylate function, pointing to different behaviours in the solid and liquid states.
Dalton Transactions 07/2007; · 3.84 Impact Factor
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ABSTRACT: A series of six new ligands (L(1)-L(6)) suitable for the formation of luminescent lanthanide complexes in water is described. Ligands L(1)-L(4) are constructed from two 6'-carboxy-6-methylene-2,2'-bipyridine chromophoric arms bonded to the amino function of a 2-aminomethylene-6-carboxy-pyridine (L(1)), an N,N-diacetate-ethylene diamine (L(2)), a serine (L(3)), or an aminomalonic acid (L(4)). For ligands L(5) and L(6), the linking amino function is provided by a glutamic acid, and the anionic functions at the 6'-position of the bipyridyl arms are made of the sodium salts of monoethylphosphonic ester (L(5)) and phosphonic acid (L(6)). The synthesis and characterisation of the ligands are described, together with the study of the formation of lanthanide complexes with europium and terbium. In the case of L(3), the europium complex obtained in acidic conditions was crystallised and the X-ray crystal structure is depicted. Photophysical properties of the complexes were studied by means of UV-visible absorption, and steady-state and time-resolved luminescence spectroscopy. Excited-state luminescence lifetimes of the complexes were determined in water and deuterated water to gain insight into the number of water molecules directly coordinated in the first coordination sphere of the complexes. The coordination behaviour of the series of ligands is questioned in the light of the spectroscopic data and discussed in terms of protection of the cation towards water molecules and their impact on the luminescence efficiency.
Chemistry 02/2007; 13(1):346-58. · 5.93 Impact Factor
