Structure regulation for ultra-high luminescence quantum yield lanthanide complex and simultaneous detection of cancer marker and ferrous ion

The exploitation of a highly selective and sensitive probe to detect both cancer marker and metal ion is of great importance.In this work,the "one stone two bird" agent of 1,10-phenanthroline(phen) is designed to disrupt the polymeric lanthanide MOFs(LnMOFs,[Ln(CHO_2)_3]n,Ln=Tb,la;Eu,1 b,CHO2=formic acid) {[Ln(CHO_2)_4·(C_2 H_8 N)]_n,Ln=Y,2 a;Gd,2 b;Dy,2 c,C_2 H_8 N=dimethylamine}) into a soluble mononuclear species [Ln(phen)2(NO_3)_3,Ln=Tb,3 a;Eu,3 b] as well as to provide an antenna for efficient photons absorption,resulting in an ultra-high luminescence quantum yield(QY,90%) europium complex.The luminescence QY is among the highest record of monomeric(zero-dimensional) lanthanide complexes.Furthermore,mononuclear Tb3+complex(3 a) functions as a multiplex sensor towards both Fe2+and cancer marker of 5-hydroxyindole-3-acetic acid(5-HIAA).Importantly,the limit of detection(LOD)for sensing 5-HIAA is an ultra-sensitive value of 1 × 10 s mol/L,which is even lower than that necessary for the early diagnosis of carcinoid tumors.More interestingly,sensing results in simulated urine reveals that 3 a has potential application for early diagnosis in the clinic.     

Association of a terpyridine ligand with lanthanide and copper(II) nitrates

Reactions between the 1,3-bis(6-methylpyridin-2-yl)pyridine ligand L, C₁₇H₁₅N₃ and Ln^III (1a, 1b, 1c, 1d) or a mixture of Ln^III and Cu^II nitrates (2a, 2b, 2c, 2d) resulted in a series of respectively novel mono- and heterodinuclear complexes, where Ln^III=Sm (a), Eu (b), Tb (c), Dy (d). The compounds were characterized by elemental analysis, ESI-MS and IR spectra, furthermore we obtained crystals of [H₂L][Eu(NO₃)₅] (1b) and [CuL₂][Eu(NO₃)₅] (2b) suitable for XRD characterization. In the crystal structures the Eu ions are 10-coordinated with quite a narrow range of Eu-O distances which are between 0.2436 and 0.2556 nm. In 1b the ligand molecule is protonated in both terminal rings, and the N-H groups are involved in the N-H···O hydrogen bonds with the same oxygen atom of one of the nitro groups. These hydrogen bonds connect the ions in 1b into the complex which is the principal building block of the structure. In 2b the [CuL₂]²⁺ counterions are present; the Cu is octahedrally coordinated by all nitrogen iatoms of two L molecules which are therefore almost perpendicular to each other. The electrostatic interactions between the charged species are in both cases the main driving force of the crystal packing.     

Enhanced afterglow performance of CaAl_2O_4:Eu~(2+),Nd~(3+) phosphors by co-doping Gd~(3+)

In order to effectively improve the afterglow properties of CaAl_2 O_4:Eu~(2+),Nd~(3+) phosphors,a series of Ca_(0.982-x)Al_2 O_4:0.012 Eu~(2+),0.006 Nd~(3+),xGd~(3+)(x=0,0.012,0.024,0.036,0.048,0.060 mol) phosphors were prepared by a high-temperature solid-phase approach.Crystalline composition and microstructure were characterized by XRD,TEM,HRTEM,and XPS,luminescence properties were systematically analyzed by fluorescence spectra,afterglow decay curves and TL glow curve.Results show that all of Ca_(0.982-x)Al_2 O_4:0.012 Eu~(2+),0.006 Nd~(3+),xGd~(3+)phosphors belong to monoclinic CaAl_2 O_4,without other cystalline phase.The blue emission at 442 nm is observed,which is assigned to the 4 f~65 d→4 f~7 transition of Eu~(2+) ions.Doping with appropriate amount of Gd~(3+) ions(x=0.036 mol) significantly improves the afterglow properties of phosphors,but the excessive doping of Gd~(3+) induces the fluorescent quenching.The doping of moderate Gd3+changes the traps states,the trap depth varies from 0.598 to 0.644 eV and the trap concentration is also greatly improved,thus significantly improving afterglow performance.     

Effect of Gd~(3+)-,Pr~(3+)-or Sm~(3+)-substituted cobalt-zinc ferrite on photodegradation of methyl orange and cytotoxicity tests

Gd~(3+)-,Pr~(3+)-or Sm~(3+)-doped Co-Zn(Co_(0.5)Zn_(0.5)Fe_2 O_4) magnetic ferrites(i.e.,Co_(0.5)Zn_(0.5)Gd_(0.1)Fe_(1.9)O_4,Co_(0.5)Zn_(0.5)Pr_(0.1)Fe_(1.9)O_4 and Co_(0.5)Zn_(0.5)Sm_(0.1)Fe_(1.9)O_4) were prepared using a facile sol-gel approach,and the structure,surface morphology and chemical composition of the products were studied by means of scanning electron microscopy(SEM),energy dispersive X-ray analysis(EDX),X-ray diffraction(XRD),UVvisible diffuse reflectance spectroscopy(DRS),photoluminescence(PL) spectroscopy,Fourier transform infrared spectroscopy(FT-IR) and vibrating sample magnetometer(VSM) spectroscopy.XRD patterns show the Co-Zn product is composed of cubic spinel phases with few impurities or secondary phases,and the average crystallite sizes of the samples are determined to be approximately～51—80,～99—181,～68—103 and～83—133 nm.Also the coercivity and remnant and saturation magnetizations,evaluated by vibrating sample magnetometer(VSM),are found to increase linearly with the incorporation of Gd3+,Pr3+and Sm3+in the product formulation.The CO_(1-x)Zn_xFe_(2-y)R_yO_4 photocatalyst sample is found to display a red shift in its absorption,and exhibits outstanding photocatalytic effects in the degradation of MO under ultraviolet(UV) light.This is attributed to the reduction of the band gap of cobalt-zinc ferrite due to the presence of rare earth ions.Further in vitro evaluations of the cytotoxic effects of the synthesized nanoparticles were performed on a HeLa cell line.     

Metal-organic frameworks of lanthanide iminodiacetates and tartrates:Synthesis,structural characterization and luminescence properties——Commemorating the 100th anniversary of the birth of Academician Guangxian Xu

Two series of lanthanide-containing metal-organic frameworks(Ln-MOFs) of the general formula{[Ln(HIDA)_2 H_2 O]ClO_4·H_2 O}_n(Ln = La(1),Nd(2),Eu(3),Gd(4),Tb(5),Eu:Tb(6);H_2 IDA=iminodiacetic acid) and [Ln(TT)(HTT)(H_2 O)_3]_n(Ln=Eu(7),Gd(8),Tb(9),Dy(10),and Eu:Tb(11);H_2 TT=tartaric acid)were synthesized by reacting Ln(ClO_4)_3 with iminodiacetic acid and L-tartaric acid,respectively.All compounds were structurally characterized by single-crystal X-ray diffraction.Elemental analyses are co nsistent with the corre sponding crystallographically generated formulas.Mo reover,the luminescence properties of both the single and mixed-lanthanide complexes were studied.Near infrared,red,and green emissions that are characteristic of Nd(Ⅲ),Eu(Ⅲ),and Tb(Ⅲ) are observed for 2,3/7,and 5/9,respectively.For the two mixed-lanthanide complex systems 6 and 11,depending on the relative amount of Eu(Ⅲ) and Tb(Ⅲ),the color of emission can be fine-tuned.It is found that a small amount of Eu(Ⅲ) is adequate for the observation of the most intense transition of Eu(Ⅲ).This is believed to be a result of energy transfer from Tb(Ⅲ) to Eu(Ⅲ) within the same complex-a conclusion supported by the significantly shortened lifetime of Tb(Ⅲ) and the accompanying enhanced lifetime of Eu(Ⅲ) in the mixedlanthanide complex with respect to the corresponding values for the pure Tb(Ⅲ) and Eu(Ⅲ) complexes with the same ligand.     

Enhanced luminescence performances of Mn~(4+)-activated Sr_4Al_(14)O_(25) red phosphors by doping with Sc~(3+) ions

A series of non-rare earth Mn⁴⁺-activated strontium aluminate phosphors Sr₄Al₁₄O₂₅:Mn⁴⁺co-doped with Sc³⁺ions were successfully synthesized by a high-temperature solid-state reaction method.XRD result reveals that there is no introduction of additional phase but expansion of lattice with incorporation of Sc34 ions.Excitation and emission spectrum measurement shows that the synthesized phosphors can be efficiently excited by near-ultraviolet and blue light,and a deep red emission centered at 652 nm with a narrow full width at half maximum(FWHM)can be obtained,which is attributed to the transition²E→⁴A₂of Mn⁴⁺ions.In addition,the crystal field strength parameter(Dq)and Racah parameters(B,C)and energies of states were calculated based on experimental data.Moreover,the luminous intensity of Sr₄Al_14-xSCxO₂₅:Mn⁴⁺is enhanced and increased by 60%compared with Mn⁴⁺single incorporated sample at x=0.06.A phenomenon of redshift is observed in the excitation spectrum and discussed systematically.Finally,the mechanism of the positive effects with Sc³⁺ions incorporated into lattice is discussed in detail.All the results suggest that the Sr₄Al_13.94Sc_0.06O₂₅:Mn⁴⁺phosphor will become one of the great candidates for backlight of LCD.     

A fluorescent probe based on a spiropyran for sensitive detection of Ce~(3+) ion

A spiropyran-based probe was developed.It serves as a fluorescence turn-on probe for selective detection of Ce~(3+) in both ethanol and aqueous(water/ethanol,1:9 or 9:1,v/v) media.Ce~(3+) can induce photochromism of the probe though the probe exhibits negligible photochromic property by itself.The probe is sensitive to Ce~(3+) and the detection limit reaches 1.7 μmol/L.It exhibits a high selectivity for Ce~(3+)ion over other common metal cations including Li~+,Na~+,Ag~+,Sr~(2+),Ni~(2+),Co~(2+),Hg~(2+),Zn~(2+),Cr~(3+),Al~(3+),Fe~(3+) and Bi~(3+) and lanthanide ions Nd~(3+),Yb~(3+) and La~(3+).The probe may be used for quantitative determination of the concentration of Ce~(3+) ion in a range of 1-10 μmol/L and for application to environmental water samples.Sensing mechanism of the probe towards Ce~(3+) ion is proposed.     

Influence of ligand architecture on the structure of coordination centre in dimeric europium carboxylates with 1,10-phenanthroline

Methods of optical spectroscopy and X-ray crystallography data were used to examine the effect of architecture of carboxylate anions on structure of the Eu³⁺ coordination centre in europium carboxylates with 1,10-phenanthroline Eu(RCOO)₃·Phen. Luminescence spectra of europium acetate, nitropropionate, benzoate, naphthylcarboxylates, phenylacetates, phenoxyacetate, triphenylpropionate were investigated. A few of europium carboxylates with 2,2′-bipyridine Eu(RCOO)₃·Bpy and europium salts Eu(RCOO)₃·nH₂O were also studied. Vibrational IR and Raman spectra of phenylacetate family were analyzed. The crystal structure of nitropropionate Eu(NO₂C₂H₄COO)₃·Phen was solved by X-ray diffraction method. The predominant influence of steric hindrances on Eu³⁺ coordination centre was observed at increase of the size of aromatic fragment of carboxylate anions. It was demonstrated, that introduction of the methylene bridges between the carboxylic group and aromatic rings of ligand weakens the effect of steric factor.     

Effect of Sr~(2+) and Dy~(3+) co-doping on coloration and temperature stabilization of a γ-Ce_2S_3 red pigment

In this paper,a Sr~(2+)and Dy~(3+)co-doped γ-Ce_2S_3 red pigment was synthesized via a combination of coprecipitation and sulfurization processes.Mixed oxide was prepared by presintering the coprecipitates,(Ce,Sr,Dy)CO_3,followed by high-temperature sulfurization under a CS_2 atmosphere.The effects of the sulfurization temperature,time,and doped proportion on the phase composition,color performance and temperature stability of γ-Ce_2S_3 were systematically studied.The results show that a stable γ-Ce_2S_3 red pigment can be obtained through Sr~(2+)and Dy~(3+)co-doping at 730℃ for 200 min.The diffraction peaks of all the samples shift to higher 2θ values with increasing doping proportion,indicating that part of the Dy~(3+)species enter the lattice and form a solid solution.The band gap of the samples remains practically constant at 2.01-2.04 eV,which causes their red color.The best red-color quality(L~*=37.13,a~*=34.77,b~*=29.44) is achieved when the pigment has a Dy~(3+)/Ce~(3+)molar ratio of 0.15,and the material maintains its excellent red color(L~*=31.49 a~*=30.94 b~*=25.33) after being heated at 410℃ for 30 min.     

Role of composition and grain size in controlling the structure sensitive magnetic properties of Sm~(3+) substituted nanocrystalline Co-Zn ferrites

The nanocrystalline samarium substituted Co-Zn ferrites with chemical formula Co_(0.7)Zn_(0.3)SmyFe_(2-y)O_4(where y=0,0.01,0.02,0.03,0.04) were synthesized by sol-gel autocombustion route.The analysis of Xray diffractograms(XRD) reveals the formation of cubic spinel structure.The planes indexed from XRD analyses were confirmed in the selected area electron diffraction(SAED) image of the sample.Nanocrystalline nature of the particles in the ferrite samples was confirmed by TEM.The morphology was analyzed by scanning electron microscopy(SEM).Magnetic measurements show an increase in the magnetization for x ≤0.03.The decrease in magnetization due to spin canting is observed for x=0.04.The coercivity depends on Sm~(3+)doping concentration,grain size and saturation magnetization.The complex permeability of the ferrites was analyzed as the function of frequency and Sm~(3+)composition(y).The real part of complex permeability varies linearly with the grain size.     

Spectroscopic investigations on Yb~(3+) doped and Pr~(3+)/Yb~(3+) codoped tellurite glasses for photonic applications

In this work we repo rt on structural and spect roscopic properties of Yb3+doped and Pr~(3+)/Yb~(3+)co-doped TeO_2-Bi_2 O_3-ZnO-Li_2 O-Nb_2 O_5(TBZLN) tellurite glasses.Bending and stretching modes of TeO_2 and Te-OH bond(strong and weak) were analysed from the deconvolution of observed Raman and FT-IR spectra.Based on the absorption measurements,the energy bands of Yb~(3+)and Pr~(3+)ions are assigned.The spectroscopic properties for the radiative transitions of Yb~(3+)and Pr~(3+)ions were reported using McCumber and Judd-Ofelt theories.Visible emission bands originating from ~3 P_1 and ~3 P_0 to lower lying levels of Pr~(3+)were registered under 447 nm excitation.The emission band around 1334 nm assigned to the Pr~3:~1 G_4→~3 H_5 was observed when excited at 980 nm.The stimulated emission cross-section(σ_(emi)(λ))and effective linewidth(Δλ_(eff)) for the ~3 P_1→~3 H_6,~3 P_1→~3 H_5,~3 P_0→~3 H_6,~3 P_0→~3 F_2,~3 P_1→~3 F_3,~3 P_1→~3 F_4,~3 P_0→~3 F_4 and ~1 G_4→~3 H_5 transitions of Pr~(3+)are reported.Upconversion luminescence in Pr~(3+)/Yb~(3+)codoped glass upon 980 nm excitation was measured.Possible resonant transfer processes between Yb~(3+)and Pr~(3+)ions are presented and discussed.The chromaticity co-ordinates were also evaluated from the visible emission spectra showing that Pr~(3+)/Yb~(3+)co-doped glass may be suitable for the development of yellow-orange(λ_(exc)=447 nm) and near white light(λ_(exc)=980 nm) emitting devices in photonics.     

Synthesis of pyrrolidinyl-ethylene fluorenyl rare-earth metal complexes and catalysis for 2-vinylpyridine polymerization

The metathesis reaction between pyrrolidinyl-ethylene fluorenyl lithium salts with in situ prepared cationic rare-earth metal dialkyl species [Ln(CH₂SiMe₃)₂(THF)_x][BPh₄] afford efficiently the corresponding constrained-geometry complexes L¹Ln(CH₂SiMe₃)₂(L¹=FluCH₂CH₂NC₄H₈,Ln=Y(1a),Lu(1b),Sc(1c)) and L² Ln(CH₂SiMe₃     

Blue-emitting Sr_(1-x)Ca_xLu_2O_4:Ce~(3+) phosphors for high CRI white LEDs

A broadband blue-emitting Sr_(1-x)Ca_xLu_2 O_4:Ce~(3+)(x=0-0.2) phospho rs were synthesized,which can be used for near-UV pumped white light-emitting diodes(w-LEDs).The crystal structures,photoluminescence pro perties,external quantum efficiency,the rmal stability and application perfo rmance of Sr_(1-x)Ca_xLu_2 O_4:Ce~(3+),by partially substituting Sr~(2+) with Ca~(2+)(x=0-0.2),were studied by various analytical techniques.When the Ca/Sr ratio of Sr_(1-x)Ca_xLu_2 O_4:Ce~(3+) gradually increases,the emission peak of Sr_(1-x)Ca_xLu_2 O_4:Ce~(3+) red-shiftes from 459 to 465 nm,corrected external quantum efficiency increases from 31.8% to 42.9%,and the thermal stability is also improved.The mechanism of the changes of the photoluminescence emission and excitation spectra,external quantum efficiency and thermal stability properties was also investigated in detail.In addition,a w-LED was fabricated by using SrLu_2 O_4:Ce~(3+)(blue),β-sialon:Eu~(2+)(green) and(Sr,Ca)AlSiN_3:Eu~(2+)(red) phosphors combined with a 405 nm near-UV LED chip,and its color rendering index(CRI) reaches 96.0.When Sr_(0.8)Ca_(0.2)Lu_2 O_4:Ce~(3+)is applied as blue phosphor to substitute SrLu_2 O_4:Ce~(3+),the obtained w-LED devices have high luminous efficiency,and CRI greater than 95.0.These re sults show that the Sr_(1-x)Ca_xLu_2 O_4:Ce~(3+) can be potential blue phosphors for n-UV pumped high CRI w-LEDs application.     

Nd~(3+)/Yb~(3+) co-doped mid-infrared luminescence fluorobromide glass with energy transfer and zero-thermal-quenching IR emission

Nd~(3+)/Yb~(3+) co-doped fluorobromide glass samples were prepared by melt quenching.The mid-infrared(MIR) luminescence of the Nd~(3+)/Yb~(3+) co-doped fluorobromide glass was investigated by Br-doping reduces the phonon state density of the matrix.The 3.9 μm MIR luminescence of the samples excited at 793 and 980 nm pump excitation was investigated in detail.There is an effective mutual energy transfer process between Nd~(3+) and Yb~(3+).It is proved under 793 nm excitation that the luminescence of Nd~(3+)at 3.9 μm is reduced by effective energy transfer from,Nd~(3+):~2 H_(11/2)→Yb~(3+):~2 F_(5/2),At the same time,it is proved that the effective energy transfer from Yb~(3+):~2 F_(5/2)→Nd~(3+):2 H_(11/2) under the excitation of 980 nm enhances the luminescence of Nd~(3+) at 3.9 μm.In addition,it is found that the samples still have good infrared(IR) luminescent properties when the temperature changes.The emission cross-sectional area and the absorption cross-sectional area are σ_(em)(3.87 × 10~(-20) cm~2) and σ_(abs)(4.25×10~(-20) cm~2).The fluorescence decay characteristics of the sample at 3.9 μm at the ~2 H_(11/2) level were investigated and the fluorescence lifetime was calculated.The gain performance of the sample was calculated and analyzed,which can reach 4.25 × 10~(-20) cm~2.Those results prove that Nd~(3+)/Yb~(3+)co-doped fluorobromide glass is the potential mid-infrared laser gain material.     

Synthesis and luminescent properties of novel pyrazolone rare earth complexes

A novel pyrazolone pyridine-containing ligand,2,6-bis(1-phenyl-4-ethoxycarbonyl-5-pyrazolone-3-yl)pyridine (H2L) was de-signed and synthesized from pyridine-2,6-dicarboxylic acid (1),and its Eu(III) and Tb(III) complexes were prepared.The ligand and com-plexes were characterized in detail based on FT-IR spectra,1H NMR,elemental analysis and thermal analysis,and the formula of Ln2L3·4H2O (Ln=Eu or Tb) of rare earth complexes was confirmed.The UV-vis absorption spectra and photoluminescence properties of the complexes were investigated,which showed that the Eu(III) and Tb(III) ions could be sensitized efficiently by the ligand (H2L) and emit the photolumi-nescence with high intensity,narrow half-peak width,and monochromic light.The results indicated that the complexes showed potential as excellent luminescent materials.     

Synthesis, crystal structures and characterization of a pair of TbIII-based enantiomers

A pair of novel Tb^III-based enantiomers, [Tb(dbm)₃·L_SS] (1) and [Tb(dbm)₃·L_RR] (2) (where L_SS=(+)-4,5-pinene bipyridine, L_RR= (-)-4,5-pinene bipyridine, dbm=dibenzoylmethanate), were synthesized and characterized based on single crystal X-ray diffraction, elemental analysis, FT-IR, TG and CD spectra. X-ray diffraction analysis showed that both the complexes crystallized in monoclinic crystal system with P2₁ chiral space group. The Tb^III ion was eight-coordinated by six O atoms of three dbm ligands and two N atoms from one chiral ligand L_SS or L_RR. The CD spectra revealed that complexes 1 and 2 were enantiomers. Thermogravimetric analysis results indicated that 1 and 2 were thermally stable up to 246 °C.     

Construction of NIR luminescent nanoscale lanthanide complexes with new flexible Schiff base ligands

Four mono-and bi-nuclear lanthanide complexes [LnL~1(No_3)(H_2O)DMF](Ln=Nd(1) and Yb(2)) and[Ln_2(L~2)_2(OAc)_2](Ln=Nd(3) and Yb(4)) were synthesized by using two new Schiff base ligands with long(CH_2)_2 NH(CH_2)_2 backbone.The lengths of the Schiff base ligands are about 1.8 nm.The bi-nuclear lanthanide complexes 3 and 4 have nanoscale structures with sizes of approximately 0.7 nm×1.1 nm×1.6 nm.For 3,the molar ratio of Nd:Br:O obtained by the energy dispersive X-ray spectroscopy analysis is in agreement with the crystal structure.The chromogenic Schiff base ligands in1-4 can efficiently transfer energy to lanthanide ions,thus,these complexes exhibit the typical NIR luminescence of lanthanide ions.Interestingly,3 and 4 have higher NIR emission quantum yields(Φ_(em))than 1 and 2,respectively.     

Tunable luminescence in co-doped Zn3Al2Ge2O10:Cr3+ by controlling crystal field splitting and nephelauxetic effect

Ce³⁺/Dy³⁺/Tb³⁺/Eu³⁺/Mn²⁺ and Cr³⁺ ions co-doped Zn₃Al₂Ge₂O₁₀ phosphor were prepared by a high-temperature solid-state method. X-ray diffraction patterns prove the cubic phase structure of prepared Zn₃Al₂Ge₂O₁₀ phosphor. Emission, excitation spectra and decay curves confirm the tunable luminescence. Different degrees of the decrease of emission FWHM in Zn₃Al₂Ge₂O₁₀:0.02Cr³⁺,RE (RE = Ce³⁺, Dy³⁺, Tb³⁺, Eu³⁺) and Zn₃Al₂Ge₂O₁₀:0.02Cr³⁺,Mn²⁺ are observed. The reason of variable FWHM is the effect of crystal field splitting and nephelauxetic effect, and the nephelauxetic effect is dominant. Therefore, the emission FWHM decreases with the increasing concentration of Mn²⁺/Tb³⁺/Eu³⁺ in Zn₃Al₂Ge₂O₁₀:0.02Cr³⁺, and for Zn₃Al₂Ge₂O₁₀:0.02Cr³⁺,Ce³⁺ and Zn₃Al₂Ge₂O₁₀:0.02Cr³⁺,Dy³⁺, it is a constant. The variation of Zn₃Al₂Ge₂O₁₀:0.02Cr³⁺,Tb³⁺ is more obvious than that of Zn₃Al₂Ge₂O₁₀:0.02Cr³⁺,Eu³⁺, because Tb³⁺ ion has smaller electronegativity. Thus, the tunable luminescence of Cr³⁺ can be realized by co-doping different ions. And these phosphors have potential applications in light-emitting diodes for plant growth.     

Preparation,structure, luminescence properties of europium doped zinc spinel structure green-emitting phosphor ZnAl2O4:Eu2+

The Zn_(1-x)Al_2 O_4:xEu~(2+) phosphor powders were synthesized by the solid-state reaction method.The synthesis temperature for ZnAl_2 O_4 was optimized,whereas the phase structure,TEM images,photoluminescence(PL) properties,the concentration quenching mechanism,the fluorescence decay curves,as well as the CIE chromaticity coordinates of the samples were investigated in details.Under the excitation at 379 nm,the phosphor exhibits an asymmetric broad-band green emission with a peak at 532 nm,which is ascribed to the 5 d-4 f transition of Eu2+.When the doping concentration of Eu2+ ions is 0.01,the luminescence intensity of the sample reaches the maximum value.It is further proved that the exchange interaction results in the concentration quenching of Eu2+ in the Zn_(1-x)Al_2 O_4:xEu~(2+) phosphor powders.The thermal quenching property of ZnAl_2 O_4:Eu~(2+)phosphor was investigated and the quantum efficiency(QE) values of the selected Zn_(0.99)Al_2 O_4:0.01 Eu~(2+) phosphor was measured and determined as 54.85%.The lifetime of the optimized sample Zn_(0.99)Al_2 O_4:0.01 Eu~(2+) is 3.0852 μs and the CIE coordinate of the sample was calculated as(0.3323,0.5538) with high-color-purity green emission.All properties indicate that the green-emitting ZnAl_2 O_4:Eu~(2+) phosphor powder has potential application in white LEDs.     

A novel terbium metal–organic framework for luminescence sensing of pyridine: Synthesis,structure, selectivity,sensitivity and recyclability

One novel two-dimensional (2D) terbium-based framework [Tb (L²⁻) (Ac) (DMA)]_n (1) (H₂L = 4'-(3,5-dicarboxyphenyl)-4,2':6′,4″-terpyridine) was successfully isolated and structurally characterized. The structural analysis reveals that two Tb³⁺ ions in 1 are bridged by two η¹:η¹:μ₂ carboxylates from L²⁻ to form a binuclear unit, which is further linked by L²⁻ to generate a 2D layer with kgd topology. Moreover, 1 displays excellent thermostability and extensive solvent stability. Luminescent measurements reveal that 1 can be used as a recyclable luminescent probe for detecting pyridine with the lowest detection limit of 0.12 vol%, and the luminescent mechanism is also discussed.