Synthesis and luminescence properties of two novel lanthanide (III) complexes of acetophenonylcarboxymethyl sulphoxide

A novel ligand containing multiple coordinating groups (sulfinyl, carboxyl and carbonyl groups), acetophenonylcarboxymethyl sulphoxide, was synthesized. Its corresponding two lanthanide (III) binary complexes were synthesized and characterized by element analysis, molar conductivity, FT‐IR, TG‐DTA and UV spectroscopy. Results showed that the composition of these complexes was REL₃L^‐ (ClO₄)₂·3H₂O (RE = Eu (III), Tb (III); L = C₆H₅COCH₂SOCH₂COOH; L^‐ = C₆H₅COCH₂SOCH₂COO^‐). FT‐IR results indicated that acetophenonylcarboxymethyl sulphoxide was bonded with an RE (III) ion by an oxygen atom of the sulfinyl and carboxyl groups and not by an oxygen atom of the carbonyl group due to high steric hinderance. Fluorescent spectra showed that the Tb (III) complex had excellent luminescence as a result of a transfer of energy from the ligand to the excitation state energy level (⁵D₄) of Tb (III). The Eu (III) complex displayed weak luminescence, attributed to low energy transfer efficiency between the triplet state energy level of its ligand and the excited state (⁵D₀) of Eu (III). As a result, the Tb (III) complex displayed a good antenna effect for luminescence. The fluorescence decay curves of Eu (III) and Tb (III) complexes were also measured. Copyright © 2012 John Wiley & Sons, Ltd.     

Preparation, crystal structure and luminescent properties of lanthanide picrate complexes with N-benzyl-2-{2′-[(benzyl-methyl-carbamoyl)-methoxy]-biphenyl-2-yloxy}-N-methyl-acetamide (L)

A new amide-based ligand derived from biphenyl, N-benzyl-2-{2′-[(benzyl-methyl-carbamoyl)-methoxy]-biphenyl-2-yloxy}-N-methyl-aceamide (L) was synthesized. Solid complexes of lanthanide picrates with this new ligand were prepared and characterized by elemental analysis, conductivity measurements, IR and electronic spectroscopies. The molecular structure of [Eu(pic)₃L] shows that the Eu(III) ion is nine-coordinated by four oxygen atoms from the L and five from two bidentate and one unidentate picrates. All the coordinate picrates and their adjacent equivalent picrates form intermolecular π-π stacking. Furthermore, the [Eu(pic)₃L] complex units are linked by the π-π stacking to form a two-dimensional (2-D) netlike supramolecule. Under excitation, the europium complex exhibited characteristic emissions. The lifetime of the ⁵D₀ level of the Eu(III) ion in the complex is 0.22 ms. The quantum yield Φ of the europium complex was found to be 1.01 × 10⁻³ with quinine sulfate as reference. The lowest triplet state energy level of the ligand indicates that the triplet state energy level of the ligand matches better to the resonance level of Eu(III) than Tb(III) ion.     

Spectroscopic investigation of europium(III) nitrato complexes in anhydrous and aqueous acetonitrile

Electronic absorption and emission spectra, along with lifetime measurements and vibrational spectra, are used to investigate the interaction between nitrate and trivalent europium ions in dilute solutions in anhydrous and aqueous acetonitrile. Upon addition of increasing quantities of nitrate, the complexes [Eu(NO₃)_n]^(3?n)+, with n = 1–5, form quantitatively in anhydrous acetonitrile. In solution, the pentanitrato species is not further solvated and its spectroscopic properties are similar to those of solid samples, indicating a similar structure with five bidentate nitrates bonded to the 10-coordinate Eu(III) ion. The lifetimes of the ⁵D₀ level are 1.35(5) and 1.25(5) ms for Eu(NO₃)₃ and (Me₄N)₂Eu(NO₃)₅ 0.05 M in CH₃CN. The quantum yield of Eu(NO₃)₃ in CH₃CN is 27.4%.The addition of small quantities of water to Eu(NO₃)₃ solutions does not result in the dissociation of the nitrate ions, provided R_w = [H₂O]_t/[Eu³⁺]_t is smaller than 8; the apparent equilibrium rations for [Eu(NO₃)₃(H₂O)_n] are K₃ = 40 ± 15 M^?1 and K₄ = 9 ± 3 M^?1; K₁ and K₂ are too large to be determined. The formation of nitrato complexes is studied in mixtures containing increasing amounts of water and nitrate. Deconvolution of the different components of the ⁵D₀ → ⁷F₀ transition allows a semi-quantitative estimate of the relative concentration of the nitrato complexes. The total number of coordinated nitrate ions per europium ion can be determined on the basis of fluorescence lifetime measurements. The apparent equilibrium ratios for the formation of the mono- and dinitrato species amount to K₁ = 23 ± 3, 15 ± 5 and 5 ± 1 for R_w = 44, 94 and 304, respectively, and to K₂ = 17 ± 8 for R_w = 44 and 94.     

Lanthanide(III) complexes of amide derivatives of DOTA exhibit an unusual variation in stability across the lanthanide series

Luminescence excitation spectroscopy of the ⁷F₀→⁵D₀ transition of the Eu(III) complex of 1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane (TCMC, an amide derivative of DOTA) is used to measure the stability constant of the complex (K). A log K value of 10.6 is obtained for [Eu(TCMC)]³⁺ at 25 °C and an ionic strength of 0.1 M. Competition experiments with eleven other members of the lanthanide(III) series give stability constants for their complexes with TCMC. An unusual variation in stability is observed for complexes of [Ln(TCMC)]³⁺ across the lanthanide series with a pronounced optimum for the Sm(III) complex. This variation is quite different from that observed for other Ln(III) macrocyclic complexes, suggesting that the TCMC ligand is uniquely sensitive to Ln(III) ion radius.     

Photoluminescence profiles and fast/slow annealing effects of Eu(III)/Tb(III)‐codoped silica phosphor materials

A silica (SiO₂) nanoparticle matrix was codoped with luminescent Eu(III) and Tb(III) ions using a modified Stöber method. The effects of fast and slow thermal annealing on photoluminescence profile imaging were examined. Slow annealing treatment suppressed more quenching sites than fast thermal annealing to further increase the photoluminescence signals. The photoluminescence signals observed between 450 and 720 nm were assigned to the ⁵D₀ → ⁷F_J (J = 0,1,2,3,4) of Eu(III) and the ⁵D₄ → ⁷F_J (J = 6,5,4,3) transitions of Tb(III). Photoluminescence was largely sensitized by indirect excitation and was much stronger than that generated by direct excitation. The Eu(III) and Tb(III) ions were doped at lower symmetry sites in the silica matrix. Copyright © 2015 John Wiley & Sons, Ltd.     

Photoluminescence imaging of europium (III)‐doped γ‐Al2O3 nanofiber structures

Aluminium oxide (Al₂O₃) has widely been used for catalysts, insulators, and composite materials for diverse applications. Herein, we demonstrated if γ‐Al₂O₃ was useful as a luminescence support material for europium (Eu) (III) activator ion. The hydrothermal method and post‐thermal treatment at 800°C were employed to synthesize Eu(III)‐doped γ‐Al₂O₃ nanofibre structures. Luminescence characteristics of Eu(III) ions in Al₂O₃ matrix were fully understood by taking 2D and 3D‐photoluminescence imaging profiles. Various sharp emissions between 580 to 720 nm were assigned to the ⁵D₀→⁷F_J (J = 0, 1, 2, 3, 4) transitions of Eu(III) activators. On the basis of X‐ray diffraction crystallography, Auger elemental mapping and the asymmetry ratio, Eu(III) ions were found to be well doped into the γ‐Al₂O₃ matrix at a low (1 mol%) doping level. A broad emission at 460 nm was substantially increased upon higher (2 mol%) Eu(III) doping due to defect creation. The first 3D photoluminescence imaging profiles highlight detailed understanding of emission characteristics of Eu(III) ions in Al oxide‐based phosphor materials and their potential applications.     

Luminescence of Eu and Ce in K3Ca2(SO4)3F fluoride material

A new halophosphor K₃Ca₂(SO₄)₃ F activated by Eu or Ce and K₃Ca₂(SO₄)₃ F:Ce,Eu co‐doped halosulfate phosphor has been synthesized by the co‐precipitation method and characterized for its photoluminescence (PL). The PL emission spectra of the K₃Ca₂(SO₄)₃ F :Ce phosphor show emission at 334 nm when excited at 278 nm due to 5d → 4f transition of Ce³⁺ ions. In the K₃Ca₂(SO₄)₃ F:Eu lattice, Eu²⁺ (440 nm) as well as Eu³⁺ (596 nm and 615 nm) emissions have been observed showing ⁵D₀ → ⁷ F₁ and ⁵D₀ → ⁷ F₂ transition of the Eu³⁺ ion, which is in the blue and red region of the visible spectrum respectively. The trivalent europium ion is very useful for studying the nature of metal coordination in various systems owing to its non‐degenerate emitting ⁵D₀ state. K₃Ca₂(SO₄)₃ F:Ce,Eu is suitable for Ce³⁺ → Eu²⁺ → Eu³⁺ energy transfer in which Ce³⁺and Eu²⁺ play the role of sensitizers and Eu²⁺ and Eu³⁺ act as the activators. The observations presented in this paper are relevant for lamp phosphors. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and optical study of Ln(III)(tetramethylurea)(AsF6)3 (Ln = LaLu,Y) and crystal structure for Ln = Eu [Eu(TMU)6(AsF6)3]

The fluorescence spectrum of Eu³⁺ recorded at a temperature of 12 K between 14.000 and 20.000 cm^?1 shows transitions from the excited stare ⁵D_o to the Stark components of the lowest ⁷F_j. The optical analysis suggests an octahedral site symmetry for the rare earth ion which is confirmed by the three-dimensional crystal determination. The highly disordered crystal structure refined in space group F23 to an R-factor of 13.2%. Both the europium and the arsenic ions are located in special positions of point symmetry 23(T). The EuO bond distance is 2.28 Å. The value of the B_q^k parameters was determined.     

Excitation and deexcitation processes of Eu(III) benzo-15-crown-5 complex studied on comparing with its first coordination sphere

The coordination sphere and the deexcitation mechanism of the Eu(III) benzo-15-crown-5 complex, Eu(B15C5), were studied with references of the Eu(III) complexes with a similar coordination sphere; the dibenzo-18-crown-6 complex, Eu₃(B₂18C6)₂, and the cryptand[2.2.1] complex, Eu([2.2.1]). NMR spectroscopy reveals that the Eu(B15C5) complex is quite stable in acetonitrile solution whereas only 40% of the Eu(III) ion forms the complex in the equimolar Eu(NO₃)₃ and B₂18C6 acetonitrile solution. The coordination sphere of the Eu(III) complexes in acetonitrile solutions were also discussed by the degenerate ⁷F₀→⁵D₀ transition energy levels. The Eu(B15C5) have a negative shift compared with the europium(III) nitrate in acetonitrile and it is explained by the coordination of both nitrate ions and the crown ether ligand. Energy transfer from the n–π* excited state located in the catechol structure to the central europium ion was first observed as the sensitized luminescence of ⁵D₀→⁷F_J. The excited state lifetime of the Eu(B15C5) complex was first determined as 201 μs in the present study.     

Rare earth complexation with 1,3,5-trideoxy-1,3,5-tris(2-hydroxybenzyl)amino-cis-inositol

The protonation constants of 1,3,5-trideoxy-1,3,5-tris(2-hydroxyl-benzyl)amino-cis-inositol (thci) in I = 1 M (NaClO₄) were determined to be: pK_a1 5.96 ± 0.03, pK_a2 7.21 ± 0.01, pK_a3 8.32 ± 0.07, pK_a4 8.95 ± 0.06. The solvent extraction studies were consistent with the formation of the Ln(thci)³⁺ and complexes. The log of the stability constants (log β₁ and log β₂) at 25 °C in 1 M (NaClO₄) at pH 4 for formation of these complexes are reported. Laser luminescence measurements of the ⁷F₀-⁵D₀ transition of Eu(III) complexed by thci indicated two species. The shifts in the peaks relative to that of Eu(aq)³⁺ were comparable to the values reported for other complexes of Eu(III) with organic ligands, but the intensities were greater. Luminescence lifetime measurements of the fluorescence spectra indicated that the complex has 5 inner sphere water molecules bound to the Eu(III) cation at pH 6.71-8.52. This was consistent with bidentate chelation of Eu(III) with each thci molecule. gaussian view energy calculations indicated bonding for M(III) to the amino and hydroxyl groups of the cyclohexanetriol and (2-hydroxybenzyl)amino moieties in the Ln(thci)³⁺ complex.     

Eu3+ (orange/red) luminescence in LiXSO4Cl (X = Mg,Zn) halosulfate phosphor

The wet chemical synthesis, X‐ray diffraction and photoluminescence characteristics in alkaline halosulfate phosphors such as LiMgSO₄Cl:Eu and LiZnSO₄Cl:Eu are reported in this paper. The effect of Li ion on Eu³⁺ luminescence (⁵D₀ → ⁷F₂ electronic transition) and incorporation of Eu³⁺ ion in lithium base alkaline halosulfate phosphor has been studied. Copyright © 2009 John Wiley & Sons, Ltd.     

Chiroptical Spectra of Tetrakis (+)‐3‐Heptafluorobutylrylcamphorate Ln(III) Complexes with an Encapsulated Alkali Metal Ion: Solution Structures as Revealed by Chiroptical Spectra

The preparation of tetrakis((+)‐hfbc) lanthanide(III) complexes with an encapsulated alkali metal and ammonium ions M[Ln((+)‐hfbc)₄] (hereafter abbreviated as M‐Ln : (+)‐hfbc, (+)‐heptafluorobutyrylcamphorate; M, ammonium or benzyl ammonium ions as well as alkali metal ions) was reported and discussed. The electronic circular dichroism (CD) spectra in the intraligand π?π* transition of M–Ln were examined in view of the solvent effect. Here, the concentration, alkali metal, and ammonium ion dependences are compared with the solid CD, ⁵D₀ ← ⁷F₀(Eu(III)) excitation spectra, circularly polarized luminescence, and vibrational circular dichroism. It has been revealed that the dodecahedral eight coordinate DD‐8‐M‐Ln complexes in crystals are equilibrated between the diastereoselectively formed square antiprism eight coordinate SAPR‐8‐M‐Ln and [Ln((+)‐hfbc)₃] in EtOH and CH₃CN solutions or between the SAPR‐8‐M‐Ln and DD‐D_2d(mmmm)‐8‐M‐Ln complexes in CHCl₃ solution. The observed CD couplets are found to reflect the exciton CD couplets which are useful to determine the four‐bladed SAPR‐(llll) absolute configuration around the lanthanide(III) ion. Chirality 24:1055–1062, 2012. © 2012 Wiley Periodicals, Inc.     

Photoluminescence properties of LiTi2 − xEux(PO4)3 phosphor

A solid‐state reaction route‐based LiTi_{2 ? x}Eu_x(PO₄)₃ was phosphor synthesized for the first time to evaluate its luminescence performance by excitation, emission and lifetime (τ) measurements. The LiTi_{2 ? x}Eu_x(PO₄)₃ phosphor was excited at λ_exci. = 397 nm to give an intense orange–red (597 nm) emission attributed to the ⁵D₀ → ⁷F₁ magnetic dipole (ΔJ = ±1) transition and red (616 nm) emission (⁵D₀ → ⁷F₂), which is an electric dipole (ΔJ = ±2) transition of the Eu³⁺ ion. Beside this, excitation and emission spectra of host LiTi₂(PO₄)₃ powder were also reported. The effect of Eu³⁺ concentration on luminescence characteristics was explained from emission and lifetime profiles. Concentration quenching in the LiTi_{2 ? x}Eu_x(PO₄)₃ phosphor was studied from the Dexter's model. Dipole–quadrupole interaction is found to be responsible for energy transfer among Eu³⁺ ions in the host lattice. The LiTi_{2 ? x}Eu_x(PO₄)₃ phosphor displayed a reddish‐orange colour realized from a CIE chromaticity diagram. We therefore suggest that this new phosphor could be used as an optical material of technological importance in the field of display devices. Copyright © 2016 John Wiley & Sons, Ltd.     

Red emissive ternary europium complexes: synthesis,optical, and luminescence characteristics

Solid ternary europium complexes consisting of fluorinated β-diketone (thenoyltrifluoroacetone, TTFA) and heteroaromatic bidentate auxiliary ligands were synthesized. The luminescence features of the complexes were estimated using various spectral measurements and clearly proved that the Eu³⁺ ion is efficiently sensitized by ligands by an antenna effect. Photoluminescence excitation spectra have shown that Eu(III) complexes are excited effectively in the ultraviolet (UV) region and the corresponding emission spectra consist of characteristic peaks attributed to the ⁵D₀→⁷F_J transitions of the europium ion with the strongest emission peak at 611 nm (⁵D₀→⁷F₂). From photoluminescence (PL) data, decay time, Judd–Ofelt parameters, transition rates, and quantum efficiency of the complexes were also determined. The Commission Internationale de l'éclairage (CIE) colour coordinates indicated the bright red emission of ternary europium complexes. Correlated colour temperature values indicated the utilization of these complexes in display devices. Judd–Ofelt and photophysical parameters were also estimated theoretically using LUMPAC software. Various frontier molecular orbitals and their respective energy were determined. These red emissive europium complexes could be utilized for fabricating solid-state lighting systems.     

Rare earth thiocyanate complexes with tripiperidinophosphine oxide: synthesis and characterization. Crystal structure of Pr(SCN)3(tpppO)3

The synthesis and characterization of rare-earth (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) thiocyanate adducts with tripiperidinophosphine oxide (tpppO) with general formula (RE)(SCN)₃(tpppO)₃ are reported. Conductance measurements in acetonitrile indicate the non-electrolytic nature of the complexes. Infrared absorption spectra evidence that the SCN⁻ ion coordinates through the nitrogen atom (isothiocyanate form) and that tpppO coordinates through the phosphoryl oxygen. X-ray powder patterns suggest the existence of three different crystal forms: (1) La; (2) an isomorphous series including Ce, Nd and Pr; and (3) another isomorphous series, including Sm, Gd, Eu, Ho, Er, Tb, Lu and Y. The visible spectra of the Nd adduct and the calculated parameters β = 0.98, b^1/2 = 0.072 and δ = 1.06 indicate that the metal-ligand bonds are essentially electrostactic. The emission spectra of the Eu compound showed ⁵D₀ → ⁷F_J bands (J = 0, 1, 2), suggesting a C_3v symmetry for the coordination polyhedron. The lifetime of the ⁵D₀ state is 1.28 ms. The emission spectra of the Tb complex presented ⁵D₄ → ⁷F_J bands (J = 4, 5, 6) and the Dy complex showed the ⁴F_9/2 → ⁶H_13/2 band. The structure of the Pr complex showed that the coordination polyhedron is a trigonal antiprism, with the isothiocyanate anions in one base and three tpppO ligands in the other. Thermal analyses (TG-DTG) were carried out for the Ce, Nd and Gd adducts. Mass losses start between 250 and 334 °C. The final residues at 1300 °C are the corresponding phosphates.     

New complexes of La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III) and Gd(III) ions with morin

New solid complex compounds of La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III) and Gd(III) ions with morin were synthesized. The molecular formula of the complexes is Ln(C₁₅H₉O₇)₃ · nH₂O, where Ln is the cation of lanthanide and n = 6 for La(III), Sm(III), Gd(III) or n = 8 for Ce(III), Pr(III), Nd(III) and Eu(III). Thermogravimetric studies and the values of dehydration enthalpy indicate that water occurring in the compounds is not present in the inner coordination sphere of the complex. The structure of the complexes was determined on the basis of UV-visible, IR, MS, ¹H NMR and ¹³C NMR analyses. It was found that in binding the lanthanide ions the following groups of morin take part: 3OH and 4CO in the case of complexes of La, Pr, Nd, Sm and Eu, or 5OH and 4CO in the case of complexes of Ce and Gd. The complexes are five- and six-membered chelate compounds.     

Formation and phosphodiesterolytic activity of lanthanide(III) N,N-bis(2-hydroxyethyl)glycine hydroxo complexes

Potentiometric titrations of N,N-bis(2-hydroxyethyl)glycine (bicine) in the presence of Ln(III) cations (Ln=La, Pr, Nd and Eu) in the pH range extended to ca. 9.5 reveal formation of two types of binuclear hydroxo complexes Ln₂(bic)₂(OH)₄ and Ln₂(bic)(OH)₄ ⁺ (bicH=bicine) in addition to previously reported mononuclear mono- and bis-complexes Ln(bic)²⁺ and Ln(bic)₂ ⁺, which predominate at pH below 8. ¹H NMR titrations of La(III)-bicine mixtures in D₂O show that the complex formation with bicine is slow in the NMR time scale and confirm formation of hydroxide rather than alkoxide complexes in basic solutions. Formation of a different type of hydroxide species under conditions of an excess of metal over ligand is confirmed by studying the absorption spectra of the Nd(III)-bicine system in the hypersensitive region. The binuclear hydroxide complexes are predominant species at pH above 9 and their stabilities increase in the order La < Pr ≈ Nd < Eu. They show fairly high catalytic activity in the hydrolysis of bis(4-nitrophenyl) phosphate (BNPP) at room temperature. Comparison of concentration and pH-dependences of the reaction rates with the species distribution diagrams shows that the catalytic hydrolysis of BNPP proceeds via a Michaelis-Menten type mechanism, which involves the Ln₂(bic)(OH)₄ ⁺ complex as the reactive species. The values of the catalytic rate constants and the Michaelis constants are in the range 0.002-0.004 s⁻¹ and 0.35-1.5 mM, respectively, for all lanthanides studied. The half-life for the hydrolysis of BNPP is reduced from 2000 years to ca. 10 min at 25 °C and pH 9.2 in the presence of 5 mM La(III) and 2.5 mM bicine.     

Lanthanide complexation with 1,3,5-triamino 2,4,6-trihydroxycyclohexane

The protonation constants of 1,3,5-triamino-2,4,6-trihydroxycyclohexane (taci), at 25 °C in I = 1.00 M (NaClO₄) were determined to be: pKa₁, 5.57 (0.08); pKa₂, 7.45 (0.02); pKa₃, 9.05 (0.04). The log of the stability constants, log β₃₀₂, at 25°C in I = 1.00 M (NaClO₄) for formation of were measured by potentiometry to be: Nd(III), 25.33 (0.09); Eu(III), 26.42 (0.06); Tm(III), 30.07 (0.10); Lu(III), 33.68 (0.07) ; Y(III), 28.59 (0.07). ¹H NMR spectra were consistent with formation of a single complex from pcH 6 to 10. Laser fluorescence measurements of the ⁷F_o-⁵D_o transition of Eu(III) complexed by taci indicated a single complexed species. The shift in this peak relative to that of Eu³⁺(aq) was significantly greater than the values reported for the complexes of other organic ligands with Eu(III). Luminescence lifetime measurements indicated two water molecules bound to each of the Eu(III) cations in the taci complex.     

Optical properties of CaAl(SO4)2Br:RE (RE = Dy,Eu, Ce) novel phosphors

A new phosphor CaAl(SO₄)₂Br doped with Dy, Ce and Eu is reported. Rare earth (Dy, Eu and Ce)‐doped polycrystalline CaAl(SO₄)₂Br phosphors were prepared using a wet chemical reaction method and studied for X‐ray diffraction and photoluminescence (PL) characteristics. Dy³⁺ emission in the CaAl(SO₄)₂Br lattice was observed at 484 and 574 nm in the blue and yellow regions of the spectrum, which are assigned to ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transitions of the Dy³⁺ ion, respectively. While the PL emission spectra of CaAl(SO₄)₂Br:Ce phosphor showed Ce³⁺ emission at 347 nm due to 5d → 4f transition of the Ce³⁺ ion. In a CaAl(SO₄)₂Br:Eu lattice, Eu³⁺ emissions were observed at 593 and 617 nm, coming from the ⁵D₀ → ⁷ F₁ and ⁵D₀ → ⁷ F₂ electron transitions, respectively. The PL study showed that the intensity of electric dipole transition at 617 nm dominates over that of magnetic dipole transition at 590 nm. The maximum PL intensity was obtained for a 1 mol% concentration of Eu³⁺ in CaAl(SO₄)₂Br host lattice. The results showed that the material may be a promising candidate as a blue‐, yellow‐ and red‐emitting phosphor. Copyright © 2013 John Wiley & Sons, Ltd.     

Remarkable chiral and luminescent properties of novel Yb(III) and Eu(III) complexes containing BINAPO ligand

Lanthanide complexes are of great importance for their prospective applications in wide range of science and technology. Chiral lanthanide complexes can constitute stereo-discriminating probes in biological media, owing to the luminescent properties of the rare-earth ions. Sensitized emission with narrow bandwidth, having fast radiation rate and high emission quantum efficiency are the main perspective for synthesizing the complexes. Attention has been given on remarkable chirality with high dissymmetry factors (g = Δε_ext/ε_max) of the complexes. For this purpose, beta-diketonato ligands with chiral BINAPO (1,1′-binapthyl phosphine oxide) ligand were chosen to achieve the goal. The complexes [Ln(TFN)₃(S-BINAPO)](TFN = 4,4,4-trifluoro-1(2-napthyl)-1,3-butanedione), [Ln(HFT)₃(S-BINAPO)] (HFT = 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedione) and [Ln(HFA)₃(S-BINAPO)](hfa = hexafluoroacetylacetonate) (where Ln = Yb, Eu) were synthesized. The complex, [Eu(TFN)₃(S-BINAPO)] gives strong red emission at 615 nm with narrow emission band (<10 nm) when excited by 465 nm light with quantum efficiency 86%. The dissymmetry factors (g = Δε_ext/ε_max) corresponding to the ⁷F₁ → ⁵D₀ transition at 590 nm is 0.091 for [Eu(TFN)₃(S-BINAPO)] and for [Yb(hfa)₃(S-BINAPO)](hfa = hexafluoroacetylacetonate) corresponding to the ²F_7/2 → ²F_5/2 transitions is 0.12, are among the largest values for both Eu and Yb complexes to date, respectively. The Eu complexes, [Eu(HFT)₃(S-BINAPO)] and [Eu(TFN)₃(S-BINAPO)] are found to be spontaneously emissive, showing bright red emission, when placed in sunlight or even in the laboratory when light is switched on.