Europium(III) complexes containing organosilyldipyridine ligands grafted on silica nanoparticles

This work focuses on the grafting of transition metal complexes on silica surface nanoparticles. Nanoscale silica particles in aqueous sols are used as starting silicated materials. We have undertaken the synthesis of europium(III) complexes containing organosilyldipyridine ligands, (EtO)3Si(CH2)3NHCH2-bipy (1) and (EtO)(CH3)2Si(CH2) 3NHCH 2-bipy (2), in view of a direct grafting reaction on silica nanoparticles. Reaction of one molar equivalent of 1 and 2 with Eu(tmhd)3 (tmhd= 2,2,6,6-tetramethyl-3,5-heptanedionato), as precursor, leads to octacoordinated silylated europium(III) complexes [Eu(tmhd)3(1)] (3) and [Eu(tmhd)3(2)] (4) as white solids in 34-54% yields. Europium complexes were characterized by elemental analysis, mass spectrometry, FT-IR, UV, and luminescence spectroscopies. These new complexes are reacting in a 1:10 (v/v) water and ethanol mixture with silica nanoparticles colloidal sol. Elemental analysis and thermogravimetric data indicated grafting ratios of 0.41 and 0.26 mmol of europium(III) complexes per gram of silica. Functionalized silica nanoparticles were characterized by DRIFT spectroscopy and TEM microscopy. The first analysis shows that the chemical integrity of the complexes is retained on the silica surface together with the size and the monodispersity of the nanoscale particles. As expected for europium(III) complexes, luminescence is observed under UV irradiation. Emission and excitation spectra indicate that the metal coordination environment is not modified on the silica surface. Moreover, the sharpness of the luminescence bands and the strong antenna effect are maintained when complexes are covalently bonded to silica. New luminescent europium(III) complexes grafted on silica nanoparticles are therefore obtained from our approach.     

烟酸稀土分子杂化发光材料的制备与性能研究

利用烯-巯加成的方法,合成了一种带有三联吡啶基团的有机硅氧烷,该中间体用核磁共振、红外、质谱等手段进行了表征确认.以该中间体作为第二配体,加入稀土(Eu3+、Tb3+)烟酸配合物,在正硅酸乙酯的存在下用溶胶-凝胶法原位制备了稀土(Eu3+、Tb3+)烟酸配合物与二氧化硅基质以共价键相连的烟酸稀土分子杂化发光材料.通过红外光谱、紫外-可见光漫反射光谱、荧光光谱和寿命测试表征了制备的杂化发光材料.荧光光谱数据表明在杂化材料中,由于三联吡啶配体通过有效的分子内传能过程将其激发态的能量传递给稀土离子的发射能级,从而极大地提高了稀土离子的特征发射.掺铕离子的最强发射为617nm,是纯红光发射;而掺铽离子的最强发射为543nm,是典型的绿光发射.掺铕和铽的分子杂化材的荧光寿命分别为0.66ms,0.68ms,同时荧光衰减均为一级指数衰减,说明稀土离子在杂化材料中分散得很均匀.     

Synthesis, characterization, and luminescence properties of the ternary europium complex covalently bonded to mesoporous SBA-15

A novel mesoporous SBA-15 type of hybrid material (phen-SBA-15) covalently bonded with 1,10-phenanthroline (phen) ligand was synthesized by co-condensation of tetraethoxysilane (TEOS) and the chelate ligand 5-[N,N-bis-3-(triethoxysilyl)propyl]ureyl-1,10-phenanthroline (phen-Si) in the presence of Pluronic P123 surfactant as a template. The preservation of the chelate ligand structure during the hydrothermal synthesis and the surfactant extraction process was confirmed by Fourier transform infrared (FTIR) and (29)Si MAS NMR spectroscopies. SBA-15 consisting of the highly luminescent ternary complex Eu(TTA)(3)phen (TTA = 2-thenoyltrifluoroacetone) covalently bonded to a silica-based network, which was designated as Eu(TTA)(3)phen-SBA-15, was obtained by introducing the Eu(TTA)(3).2H(2)O complex into the hybrid materials via a ligand exchange reaction. XRD, TEM, and N(2) adsorption measurements were employed to characterize the mesostructure of Eu(TTA)(3)phen-SBA-15. For comparison, SBA-15 doped with Eu(TTA)(3).2H(2)O and Eu(TTA)(3)phen complexes and SBA-15 covalently bonded with a binary europium complex with phen ligand were also synthesized, and were named SBA-15/Eu(TTA)(3), SBA-15/Eu(TTA)(3)phen, and Eu-phen-SBA-15, respectively. The detailed luminescence studies on all the materials showed that, compared with the doping sample SBA-15/Eu(TTA)(3)phen and binary europium complex functionalized sample Eu-phen-SBA-15, the Eu(TTA)(3)phen-SBA-15 mesoporous hybrid material exhibited higher luminescence intensity and emission quantum efficiency. Thermogravimetric analysis on Eu(TTA)(3)phen-SBA-15 demonstrated that the thermal stability of the lanthanide complex was evidently improved as it was covalently bonded to the mesoporous SBA-15 matrix.     

Fabrication and luminescent properties of Eu(BMPPA)3BPy complex and its functionalized silica nanocomposites

Luminescent silica nanocomposites functionalized with a Eu-complex have been prepared and characterized.The europium complex is composed of 2,2'-bipyridyl(BPy) and 2-(4-bromomethyI)-phenylpropionic acid(BMPPA),which contains highly active benzyl bromide substituents and can covalently bind with poly(4-vinylpyridine)(P4VP)-modified silica nanoparticles(nanoSiO_2P4VP) to form nanoSiO_2P4VPEuBPy composites.Microscopic images revealed that the nanoSiO_2P4VPEuBPy composites easily formed aggregates,due to an inter-particle binding caused by the benzyl bromide among the composites.The as-prepared nanocomposites showed the typical emissions of Eu(III) ions at the wavelengths from 580 nm to 750 nm designated to the ~5D_0→~7F_n transitions.Time-resolved fluorescence decay measurements revealed that the emission lifetime was approximately 0.204 ms and 0.576 ms for the nanoSiO_2EuBPy composites,a little shorter than that in the Eu(BMPPA)_3BPy complex.     

Reversible modulation in luminescence intensity of a single vesicle composed of diblock azo-copolymer and tris(dibenzoylmethanate)(phenanthroline)europium(III)

Tris(dibenzoylmethanate)(phenanthroline)europium(III)[Eu(DBM)(3)Phen]-doped amphiphilic vesicles were obtained by self-assembling of poly(N-isopropylacrylamide)-b-poly[6-[4-(4-methylphenyl-azo) phenoxy] hexylacrylate] (PNIPAM(83)-b-PAzoM(20)) in presence of Eu(DBM)(3)Phen in the mixed solvent of THF/H(2)O (50/50 vol.%). Their optical properties were studied by UV-vis and fluorescence spectroscopies. The UV-vis spectrum showed that the electronic transition bands of azobenzene and Eu(DBM)(3)Phen were overlapped at about 365 nm and the main peak of fluorescence emission band appeared at 612 nm. So the vesicles showed obvious red luminescence. It was found that the fluorescence intensity of a single Eu(DBM)(3)Phen-doped vesicle could be modulated by irradiation with UV and visible light due to the reversible trans-cis-trans photoisomerization reaction of azobenzene moiety. Possible energy allocation process for this property was discussed in details.     

Highly luminescent, triple- and quadruple-stranded, dinuclear Eu, Nd, and Sm(III) lanthanide complexes based on bis-diketonate ligands

The bis(beta-diketone) ligands 1,3-bis(3-phenyl-3-oxopropanoyl)benzene, H(2)L(1) and 1,3-bis(3-phenyl-3-oxopropanoyl) 5-ethoxy-benzene, H(2)L(2), have been prepared for the examination of dinuclear lanthanide complex formation and investigation of their properties as sensitizers for lanthanide luminescence. The ligands bear two conjugated diketonate binding sites linked by a 1,3-phenylene spacer. The ligands bind to lanthanide(III) or yttrium(III) ions to form neutral homodimetallic triple stranded complexes [M(2)L(1)(3)] where M = Eu, Nd, Sm, Y, Gd and [M(2)L(2)(3)], where M = Eu, Nd or anionic quadruple-stranded dinuclear lanthanide units, [Eu(2)L(1)(4)](2-). The crystal structure of the free ligand H(2)L(1) has been determined and shows a twisted arrangement of the two binding sites around the 1,3-phenylene spacer. The dinuclear complexes have been isolated and fully characterized. Detailed NMR investigations of the complexes confirm the formation of a single complex species, with high symmetry; the complexes show clear proton patterns with chemical shifts of a wide range due to the lanthanide paramagnetism. Addition of Pirkle's reagent to solutions of the complexes leads to splitting of the peaks, confirming the chiral nature of the complexes. Electrospray and MALDI mass spectrometry have been used to identify complex formulation and characteristic isotope patterns for the different lanthanide complexes have been obtained. The complexes have high molar absorption coefficients (around 13 x 10(4) M(-1)cm(-1)) and display strong visible (red or pink) or NIR luminescence upon irradiation at the ligand band around 350 nm, depending on the choice of the lanthanide. Emission quantum yield experiments have been performed and the luminescence signals of the dinuclear complexes have been found to be up to 11 times more intense than the luminescence signals of the mononuclear analogues. The emission quantum yields and the luminescence lifetimes are determined to be 5% and 220 micros for [Eu(2)L(1)(3)], 0.16% and 13 micros for [Sm(2)L(1)(3)], and 0.6% and 1.5 micros for [Nd(2)L(1)(3)]. The energy level of the ligand triplet state was determined from the 77 K spectrum of [Gd(2)L(1)(3)]. The bis-diketonate ligand is shown to be an efficient sensitizer, particularly for Sm and Nd. Photophysical studies of the europium complexes at room temperature and 77 K show the presence of a thermally activated deactivation pathway, which we attribute to ligand-to-metal charge transfer (LMCT). Quenching of the luminescence from this level seems to be operational for the Eu(III) complex but not for complexes of Sm(III) and Nd(III), which exhibit long lifetimes. The quadruple-stranded europium complex has been isolated and characterized as the piperidinium salt of [Eu(2)L(1)(4)](2-). Compared with the triple-stranded Eu(III) complex in the solid state, the quadruple-stranded complex displays a more intense emission signal with a distinct emission pattern indicating the higher symmetry of the quadruple-stranded complex.     

Highly luminescent bis-diketone lanthanide complexes with triple-stranded dinuclear structure

A new bis-β-diketone, 3,3'-bis(4,4,4-trifluoro-1,3-dioxobutyl)biphenyl (BTB), has been designed and prepared for the synthesis of a series of dinuclear lanthanide complexes [Ln(2)(BTB)(3)(C(2)H(5)OH)(2)(H(2)O)(2)] [Ln = Eu (1), Gd (2)], [Ln(2)(BTB)(3)(DME)(2)] [Ln = Nd (3), Yb (4); DME = ethylene glycol dimethyl ether] and [Eu(2)(BTB)(3)(L)(2)] [L = 2,2-bipydine (5); 1,10-phenanthroline (6); 4,7-diphenyl-1,10-phenanthroline (7)]. Complexes 1-7 have been characterized by various spectroscopic techniques and their photophysical properties are investigated. X-ray crystallographical analysis reveals that complexes 1, 3 and 4 adopt triple-stranded dinuclear structures which are formed by three bis-bidentate ligands with two lanthanide ions. The complexes 1 and 3-7 display strong visible red or NIR luminescence upon irradiation at ligand band around 372 nm, depending on the choice of the lanthanide. The solid-state photoluminescence quantum yields and the lifetimes of Eu(3+) complexes are determined and described.     

Rare-Earth complexes of ferrocene-containing ligands: visible-light excitable luminescent materials

The ferrocene-derivatives bis(ferrocenyl-ethynyl)-1,10-phenanthroline (Fc(2)phen) and ferrocenoyltrifluoroacetone (Hfta) have been used to synthesize ferrocene-containing rare-earth beta-diketonate complexes. The complexes [Ln(tta)(3)(Fc(2)phen)] and [Ln(fta)(3)(phen)] (where Ln = La, Nd, Eu, Yb) show structural similarities to the tris(2-thenoyltrifluoroacetonate)(1,10-phenanthroline)lanthanide(III) complexes, [Ln(tta)(3)(phen)]. The coordination number of the lanthanide ion is 8, and the coordination sphere can be described as a distorted dodecahedron. However, the presence of the ferrocene moieties shifts the ligand absorption bands of the rare-earth complexes to longer wavelengths so that the complexes can be excited not only by ultraviolet radiation but also by visible light of wavelengths up to 420 nm. Red photoluminescence is observed for the europium(III) complexes and near-infrared photoluminescence for the neodymium(III) and ytterbium(III) complexes. The presence of the ferrocene groups makes the rare-earth complexes hydrophobic and well-soluble in apolar organic solvents.     

Electrochemical and electrochemiluminescence study of Ru(bpy)(2+)3-doped silica nanoparticles with covalently grafted biomacromolecules

Spherical Ru(bpy)(2+)(3)-doped silica (RuSi) nanoparticles were prepared via a water-in-oil microemulsion approach. The electrochemical and electrochemiluminescent properties of the RuSi nanoparticles immobilized on an indium tin oxide (ITO) electrode were investigated. Further, electrochemiluminescence (ECL) of the RuSi nanoparticles with covalently coated biomacromolecules was studied. By covalent cross-linking with glutaraldehyde, gamma-(aminopropyl) triethoxysilane (APTES)-pretreated RuSi nanoparticles were coupled with different concentrations of bovine serum albumin (BSA), hemoglobin, and myoglobin, respectively. ECL from these biomacromolecule-coated RuSi nanoparticles decreased with the increase of the loading of biomacromolecules. Moreover, the ECL of coreactants with different sizes was studied. The ECL decrease could be assigned to the steric hindrance and limited diffusion of coreactant molecules into the RuSi nanoparticles after biomacromolecule conjugation. Since tens of thousands of Ru(bpy)(2+)(3) molecules are contained in the silica particles and the RuSi nanoparticle surface modification could improve their biocompatibility, the biomacromolecule-coated RuSi nanoparticles could be readily used as efficient and stable ECL tag materials in the future.     

Luminescent ruthenium(II) bipyridine-calix[4]arene complexes as receptors for lanthanide cations

The synthesis and photophysical properties of novel luminescent ruthenium(II) bipyridyl complexes containing one, two, or six lower rim acid-amide-modified calix[4]arene moieties covalently linked to the bipyridine groups are reported which are designed to coordinate and sense luminescent lanthanide ions. All the Ru-calixarene complexes synthesized in this work are able to coordinate Nd(3+), Eu(3+), and Tb(3+) ions with formation of adducts of variable stoichiometry. The absorbance changes allow the evaluation of association constants whose magnitudes depend on the nature of the complexes as well as on the nature of the lanthanide cation. Lanthanide cation complex formation affects the ruthenium luminescence which is strongly quenched by Nd(3+) ion, moderately quenched by the Eu(3+) ion, and poorly or moderately increased by the Tb(3+) ion. In the case of Nd(3+), the excitation spectra show that (i) the quenching of the Ru luminescence occurs via energy transfer and (ii) the electronic energy of the excited calixarene is not transferred to the Ru(bpy)(3) but to the neodymium cation. In the case of Tb(3+), the adduct's formation leads to an increase of the emission intensities and lifetimes. The reason for this behavior was ascribed to the electric field created around the Ru calix[4]arene complexes by the Tb(3+) ions by comparison with the Gd(3+) ion, which behaves identically and can affect ruthenium luminescence only by its charge. However, especially for compounds 1 and 3, it cannot be excluded that some contribution comes from the decrease of vibrational motions (and nonradiative processes) due to the rigidification of the structure upon Tb(3+) complexation. In the case of Eu(3+), compounds 1, 2, and 4 were quenched by the lanthanide addition but the quenching of the ruthenium luminescence is not accompanied by europium-sensitized emission which suggests that an electron-transfer mechanism is responsible for the quenching. On the contrary, compound 3 exhibits enhanced emission upon addition of Eu(3+) (as nitrate salt); it is suggested that the lack of quenching in the [3.2Eu(3+)] adduct is due to kinetic reasons because the electron-transfer quenching process is thermodynamically allowed.     

Preparation of hybrid mesoporous silica luminescent nanoparticles with lanthanide(III) complexes and their exhibition of white emission

We chose dipicolinic acid as a tridentate chelating unit featuring ONO donors to react with lanthanide(III) ions to yield tight and protective N(3)O(6) environments around the lanthanide(III) ions. We immobilized the lanthanide(III)-dipicolinic acid complexes on colloidal mesoporous silica with diameter smaller than 100 nm by a covalent bond grafting technique and obtained nearly monodisperse luminescent Eu-dpa-Si and Tb-dpa-Si functionalized hybrid mesoporous silica nanomaterials. These hybrid nanomaterials were characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, nitrogen adsorption-desorption, and photoluminescence spectroscopic techniques. The hybrid mesoporous silica nanoparticles exhibit intense emission lines upon UV-light irradiation, owing to the effective intramolecular energy transfer from the chromophore to the central lanthanide Eu(3+) and Tb(3+) ions. Furthermore, the functionalized nanomaterials can be turned to white light materials after annealing at high temperature.     

Anion/cation induced optical switches based on luminescent lanthanide (Tb3+ and Eu3+) hydrogels

Two novel silica based lanthanide complexes (Tb(a)(2) and Eu(a)(2)) were encapsulated into poly(acrylic acid) host. Both Tb(III) and Eu(III) containing hydrogels have typical and easily distinguished narrow line emissions occurring in the green and red region respectively. Particularly, the excitation wavelength for Eu complex can be extended into nearly visible light range (λ(ex) = 395 nm). Interestingly, we discover that these target materials not only exhibit selective emission response towards HSO(4)(-) (detection limit 10(-5) M) compared with CH(3)COO(-), F(-), Cl(-), Br(-) and I(-) but also give unique quenching to Cu(2+) (detection limit 10(-5) M) (tested cations: Cu(2+), Pd(2+), Cd(2+), Co(2+) and Mn(2+)). More importantly, this kind of materials can be recycled more than 10 times.     

Optical spectroscopy study of organic-phase lanthanide complexes in the TALSPEAK separations process

Time-resolved fluorescence spectroscopy and Fourier transform IR spectroscopy have been applied to characterize the coordination environment of lipophilic complexes of Eu(3+) with bis(2-ethylhexyl)phosphoric acid (HDEHP) and (2-ethylhexyl)phosphonic acid mono(2-ethylhexyl) ester (HEH[EHP]) in 1,4-diisopropylbenzene (DIPB). The primary focus is on understanding the role of lactate (HL) in lanthanide partitioning into DIPB solutions of HDEHP or HEH[EHP] as it is employed in the TALSPEAK solvent extraction process for lanthanide separations from trivalent actinides. The broader purpose of this study is to characterize the changes that can occur in the coordination environment of lanthanide ions as metal-ion concentrations increase in nonpolar media. The optical spectroscopy studies reported here complement an earlier investigation of similar solutions using NMR spectroscopy and electrospray ionization mass spectrometry. Emission spectra of Eu(3+) complexes with HDEHP/HEH[EHP] demonstrate that, as long as the Eu(3+) concentration is maintained well below saturation of the organic extractant solution, the Eu(3+) coordination environment remains constant as both [HL](org) and [H(2)O](org) are increased. If the total organic-phase lanthanide concentration is increased (by extraction of moderate amounts of La(3+)), the (5)D(0) → (7)F(1) transition singlet splits into a doublet with a notable increase in the intensity of both (5)D(0) → (7)F(1) and (5)D(0) → (7)F(2) electronic transitions. The increased multiplicity in the emission spectra indicates that Eu(3+) ions are present in multiple coordination environments. The increased emission intensity of the 614 nm band implies an overall reduction in symmetry of the extracted Eu(3+) complex in the presence of macroscopic La(3+). Although [H(2)O](org) increases to above 1 M at high [HL](tot), this water is not associated with the Eu(3+) metal center. IR spectroscopy results confirm a direct Ln(3+)-lactate interaction at high concentrations of lanthanide and lactate in the extractant phase. At low organic-phase lanthanide concentrations, the predominant complex is almost certainly the well-known Ln(DEHP·HDEHP)(3). As lanthanide concentrations in the organic phase increase, mixed-ligand complexes with the general stoichiometry Ln(L)(n)(DEHP)(3-n) or Ln(L)(n)(DEHP·HDEHP)(3-n) become the dominant species.     

Near-infrared luminescent hybrid materials doped with lanthanide (Ln) complexes (Ln = Nd, Yb) and their possible laser application

The crystal structures of ternary Ln(DBM)(3)phen complexes (DBM = dibenzoylmethane, phen = 1,10-phenanthroline, and Ln = Nd, Yb) and their in situ syntheses via the sol-gel process are reported. The properties of the Ln(DBM)(3)phen complexes and their corresponding Ln(3+)/DBM/phen-co-doped luminescent hybrid gels obtained via an in situ method (Ln-D-P gel) have been studied. The results reveal that the lanthanide complexes are successfully in situ synthesized in the corresponding Ln-D-P gels. Both Ln(DBM)(3)phen complexes and Ln-D-P gels display sensitized near-infrared (NIR) luminescence upon excitation at the maximum absorption of the ligands, which contributes to the efficient energy transfer from the ligands to the Ln(3+) ions (Ln = Nd, Yb), an antenna effect. The radiative properties of the Nd(3+) ion in a Nd-D-P gel are discussed using Judd-Ofelt analysis, which indicates that the (4)F(3/2) --> (4)I(11/2) transition of the Nd(3+) ion in the Nd-D-P gel can be considered as a possible laser transition.     

Development of a zinc ion-selective luminescent lanthanide chemosensor for biological applications

Detection of chelatable zinc (Zn(2+)) in biological studies has attracted much attention recently, because chelatable Zn(2+) plays important roles in many biological systems. Lanthanide complexes (Eu(3+), Tb(3+), etc.) have excellent spectroscopic properties for biological applications, such as long luminescence lifetimes of the order of milliseconds, a large Stoke's shift of >200 nm, and high water solubility. Herein, we present the design and synthesis of a novel lanthanide sensor molecule, [Eu-7], for detecting Zn(2+). This europium (Eu(3+)) complex employs a quinolyl ligand as both a chromophore and an acceptor for Zn(2+). Upon addition of Zn(2+) to a solution of [Eu-7], the luminescence of Eu(3+) is strongly enhanced, with high selectivity for Zn(2+) over other biologically relevant metal cations. One of the important advantages of [Eu-7] is that this complex can be excited with longer excitation wavelengths (around 340 nm) as compared with previously reported Zn(2+)-sensitive luminescent lamthanide sensors, whose excitation wavelength is at too high an energy level for biological applications. The usefulness of [Eu-7] for monitoring Zn(2+) changes in living HeLa cells was confirmed. This novel Zn(2+)-selective luminescent lanthanide chemosensor [Eu-7]should be an excellent lead compound for the development of a range of novel luminescent lanthanide chemosensors for biological applications.     

Luminescent nanoparticles prepared by encapsulating lanthanide chelates to silica sphere

The luminescent nanoparticles were prepared by encapsulating the [LnL₄]^? (Ln = Eu, Tb; L = BTFA, HFAA, TTFA, TFAA) complexes anion into the silicon framework. We firstly synthesized a series of novel siloxy-bearing lanthanide complex precursor, and then encapsulated them into the silica sphere by a modified Stöber process. As a result, four europium and two terbium tetrakis β-diketonate complexes functionalized silica sphere nanoparticles were obtained and characterized in detail using Fourier transform infrared spectra, X-ray diffraction, scanning electronic microscope, thermogravimetric analysis, luminescence excitation and emission spectroscopy, luminescence lifetime measurements, and diffuse reflectance UV–Vis spectroscopy. The result shows that these luminescent nanoparticles maintain the distinctive luminescence character of lanthanide chelate including broad excitation spectra, line-like emission spectra, high quantum efficiency, and long luminescent lifetime, which makes them great potential application in the synthesis of luminescent nanoparticle.     

Synthesis and photophysical characterization of highly luminescent silica films doped with substituted 2-hydroxyphthalamide (IAM) terbium complexes

Innovative Tb(3+) antenna complexes employing two different substituted 2-hydroxyphthalamide ligands (HxOH-IAM and bis-HxOH-IAM) acting simultaneously as coordinating sites and light collector units have been synthesized and successively anchored in silica layers by the sol-gel technique. The complexes show remarkable photoluminescence (PL) quantum yields in methanol solution, as high as 0.30 and 0.40 for (HxOH-IAM)(4)?Tb(3+) and (bis-HxOH-IAM)(2)?Tb(3+), respectively. The grafting of the Tb(3+) complexes in silica single layers accomplished by exploiting the terminal hydroxyl groups of the IAM chains results in highly transparent and homogeneous films displaying bright green emission and PL efficiencies of up to 0.40. The silica layers containing the (bis-HxOH-IAM)(2)?Tb(3+) show remarkable photostability even under prolonged and continuous irradiation (up to 3.5 h). The nature of the IAM ligands allows the photoexcitation of the complexes at wavelengths even longer than 350 nm, which is a spectral window suitable to develop luminescent lanthanide probes dedicated to bioanalyses and bioimaging applications.     

Syntheses,crystal structures,and luminescent properties of lanthanide complexes with tripodal ligands bearing benzimidazole and pyridine groups

Two tripodal ligands, bis(2-benzimidazolylmethyl)(2-pyridylmethyl)amine (L(1)) and bis(2-pyridylmethyl)(2-benzimidazolylmethyl)amine (L(2)), were synthesized. With the third chromophoric ligand antipyrine (Antipy), three series of lanthanide(III) complexes were prepared: [LnL(1)(Antipy)(3)](ClO(4))(3) (series A), [LnL(1)(Antipy)Cl(H(2)O)(2)]Cl(2)(H(2)O)(2) (series B), and [LnL(2)(NO(3))(3)] (series C). The nitrate salt of the free ligand H(2)L(1).(NO(3))(2) and six complexes were structurally characterized: Pr(3+)A, Y(3+)A, Eu(3+)B, Eu(3+)C, Gd(3+)C and Tb(3+)C, in which the two A and three C complexes are isomorphous. Crystallographic studies showed that tripodal ligands L(1) and L(2) exhibited a tripodal coordination mode and formed 1:1 complexes with all lanthanide metal ions. The coordination numbers of the lanthanide metal ions for the A, B, and C complexes were 7, 8, and 10, respectively. Conductivity studies on the B and C complexes in methanol showed that, in the former, the coordinated Cl(-) dissociated to give 3:1 electrolytes and, in the latter, two coordinated NO(3)(-) ions dissociated to give 2:1 electrolytes. Detailed photophysical studies have been performed on the free ligands and their Gd(III), Eu(III), and Tb(III) complexes in several solvents. The results show a wide range in the emission properties of the complexes, which could be rationalized in terms of the coordination situation, the (3)LC level of the complexes, and the subtle variations in the steric properties of the ligands. In particular the Eu(3+)A and Tb(3+)A complexes, in which the central metal ions were wholly coordinated by chromophoric ligands of one L(1) and three antipyrine molecules, had relatively higher emission quantum yields than their corresponding B and C complexes.     

Luminescence tuning of imidazole-based lanthanide(III) complexes [Ln = Sm, Eu, Gd, Tb, Dy

To tune the lanthanide luminescence in related molecular structures, we synthesized and characterized a series of lanthanide complexes with imidazole-based ligands: two tripodal ligands, tris{[2-{(1-methylimidazol-2-yl)methylidene}amino]ethyl}amine (Me(3)L), and tris{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine (H(3)L), and the dipodal ligand bis{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine (H(2)L). The general formulas are [Ln(Me(3)L)(H(2)O)(2)](NO(3))(3)·3H(2)O (Ln = 3+ lanthanide ion: Sm (1), Eu (2), Gd (3), Tb (4), and Dy (5)), [Ln(H(3)L)(NO(3))](NO(3))(2)·MeOH (Ln(3+) = Sm (6), Eu (7), Gd (8), Tb (9), and Dy (10)), and [Ln(H(2)L)(NO(3))(2)(MeOH)](NO(3))·MeOH (Ln(3+) = Sm (11), Eu (12), Gd (13), Tb (14), and Dy (15)). Each lanthanide ion is 9-coordinate in the complexes with the Me(3)L and H(3)L ligands and 10-coordinate in the complexes with the H(2)L ligand, in which counter anion and solvent molecules are also coordinated. The complexes show a screw arrangement of ligands around the lanthanide ions, and their enantiomorphs form racemate crystals. Luminescence studies have been carried out on the solid and solution-state samples. The triplet energy levels of Me(3)L, H(3)L, and H(2)L are 21?000, 22?700, and 23?000 cm(-1), respectively, which were determined from the phosphorescence spectra of their Gd(3+) complexes. The Me(3)L ligand is an effective sensitizer for Sm(3+) and Eu(3+) ions. Efficient luminescence of Sm(3+), Eu(3+), Tb(3+), and Dy(3+) ions was observed in complexes with the H(3)L and H(2)L ligands. Ligand modification by changing imidazole groups alters their triplet energy, and results in different sensitizing ability towards lanthanide ions.     

Experimental and theoretical approaches toward anion-responsive tripod-lanthanide complexes: mixed-donor ligand effects on lanthanide complexation and luminescence sensing profiles

A new series of tripods were designed to form anion-responsive, luminescent lanthanide complexes. These tripods contain pyridine, thiazole, pyrazine, or quinoline chromophores combined with amide carbonyl oxygen and tertiary nitrogen atoms. Crystallographic and EXAFS studies of the 10-coordinated tripod-La(NO(3))(3) complexes revealed that each La(3+) cation was cooperatively coordinated by one tetradentate tripod and three bidentate NO(3)(-) anions in the crystal and in CH(3)CN. Quantum chemical calculations indicated that the aromatic nitrogen plays a significant role in lanthanide complexation. The experimentally determined stability constants of complexes of the tripod with La(NO(3))(3), Eu(NO(3))(3), and Tb(NO(3))(3) were in good agreement with the theoretically calculated interaction energies. Complexation of each tripod with lanthanide triflate gave a mixture of several lanthanide complex species. Interestingly, the addition of a coordinative NO(3)(-) or Cl(-) anion to the mixture significantly influenced the lanthanide complexation profiles. The particular combination of tripod and a luminescent Eu(3+) center gave anion-selective luminescence enhancements. Pyridine-containing tripods exhibited the highest NO(3)(-) anion-selective luminescence and thus permit naked-eye detection of the NO(3)(-) anion.