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.     

Synthesis, crystal structure and characterization of one-dimension complex constructed by terbium（III） and 2-iodobenzoate

The complex of [Tb(2-IBA)₃(H₂O)₂]_n (2-IBA=2-iodobenzoate)was prepared by solvent method from TbCl₃·6H₂O and 2-iodobenzoic acid. The crystal structure was determined with X-ray single-crystal diffraction. The X-ray diffraction analysis indicated that the title complex crystallized in triclinic crystal system and Pī space group. The Tb³⁺ ion was coordinated by six oxygen atoms from five 2-IBA ligands and two oxygen atoms from two water molecules, giving a distorted square-antiprism polyhedral geometry. The carboxyl groups were bonded to the Tb³⁺ ions with bidentate-bridging and bidentate-chelating coordination modes. The adjacent Tb³⁺ ions were linked by two bidentate-bridging 2-IBA ligands, forming 1-D chain structure. The fluorescence spectrum of the complex showed four main peaks at 489, 543, 587, and 618 nm, corresponding to ⁵D₄→⁷F_J (J=6?3) transition emissions of the Tb³⁺ ion, respectively.     

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.     

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.     

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, characterization and enhanced luminescence of terbium complexes with 2-pyrazinecarboxylic acid and butanedioic acid by inert-fluorescent lanthanide ions

Ten solid terbium complexes with 2-pyrazinecarboxylic acid (Hpyca) and butanedioic acid (BDAH) were synthesized via coprecipitation method and characterized by elemental, EDTA titration, inductively coupled plasma (ICP), thermogravimetry-differential scanning calorimetry (TG-DSC) and infrared (IR) analyses. The results showed that the complexes had the compositions of Tb(pyca)(BDA)·2H2O, Tb0.5Y0.5(pyca)(BDA)·2H2O, Tb0.5La0.5(pyca)(BDA)·3H2O, Tb0.5Gd0.5(pyca)(BDA)·2H2O, Tb0.7Y0.3(pyca)(BDA)·3H2O, Tb0.7La0.3(pyca)(BDA)·0.5H2O, Tb0.7Gd0.3(pyca)(BDA)·H2O, Tb0.6Y0.4(pyca)(BDA)·2.5H2O, Tb0.6La0.4 (pyca)(BDA)·2.5H2O and Tb0.6Gd0.4(pyca)(BDA)·3H2O. IR spectra indicated that the rare earth ions coordinated with the carboxylic oxygen atoms of Hpyca and BDAH. Luminescence spectra showed that the doped La3+, Y3+ or Gd3+ ions did not affect the luminescence emission peak positions, but remarkably increased the luminescent intensities of terbium complexes. Furthermore, the doped lanthanide complexes showed longer luminescence lifetimes and higher quantum yields than pure terbium complex. The enhanced luminescence efficiencies of Tb3+ ions in the doped complexes might result from the antenna effect of the two carboxylate ligands as well as the decrease of the self-quench of the Tb3+ ions induced by the doped lanthanide ions.     

Synthesis,photoluminescence properties and thermal investigation by TG-MS of RE(DAS)_3·xH_2O(RE=Eu~(3+),Tb~(3+))

Rare earth(Ⅲ) diphenyl-4-amine sulfonates(RE(DAS)_3·xH_2O,RE=Eu~(3+),Tb~(3+))phosphors were synthesized by precursor method from barium diphenyl-4-amine sulfonate and rare earth sulfates.FTIR,TG/DSC coupled to mass spectrometry(TG/DSC/MS),X-ray powder diffraction(XPD),scanning electron microscopy(SEM) and photo luminesce nce(PL) spectroscopy were utilized to structurally and morphologically characterize the samples.Thermal decomposition of Eu(DAS)_3·7H_2O and Tb(DAS)_3·2H_2O at 973 K under dynamic air atmosphere results in crystalline Eu_2O_2SO_4 and Tb_2O_2SO_4 materials,respectively.Accordingly,MS spectra reveal the liberation of thermal decomposition products of precursors,largely as CO_2,NO_2 and SO_2 gases.The diphenyl-4-amine sulfonate(DAS) ligand demonstrats a good stabilizing property for Eu~(3+) and Tb~(3+) ions.The Eu(DAS)_3·7H_2O and Tb(DAS)_3·2H_2O compounds display efficient red and green emissions,under UV excitation,arising from the ~5D_0→~7F_J(J=0-4) and ~5D_4→~7F_J(J=0-6) transitions of the Eu~(3+) and Tb~(3+) ions,respectively.     

Hydrothermal synthesis and structural studies of a new coordination polymer of lanthanum（III） with benzene-1,2,4,5-tetracarboxylic acid and 4,4＇-bipyridine

A new lanthanum complex formulated as {(bpyH₂)[La(btc)(H₂O)₄(NO₃)]·2H₂O}_n (1) (btcH₄=benzene-1,2,4,5-tetracarboxylic acid; bpy=4,4′-bipyridine) was hydrothermally synthesized. The complex was characterized by FT-IR spectroscopy, elemental analysis and X-ray diffraction. X-ray crystal structural analysis revealed that the compound belonged to the monoclinic space group C2/c with cell parameters a= 1.42806(7) nm, b=1.10258(5) nm, c=1.60333(8) nm and β=101.9400(10)°. The complex was polymeric with La^III atoms linked by four O atoms from two carboxylate groups of one benzene-1,2,4,5-tetracarboxylate. The La^III atom was ten coordinated in a distorted tetracapped trigonal prism. In the crystal structure, a wide range of noncovalent interactions consisting of hydrogen bonding (of the types of O—H…O, N—H…O and C—H…O) and ion pairing interactions connected the various components into a supramolecular structure.     

Application of three Ln(Ⅲ)-coordination polymers in fields of luminescence,antibacteria and detection of Fe3+ and 4-nitrophenol

Three lanthanide-based coordination polymers(Ln-CPs) with layered structure,{[La₂(L)₃(DMF)(H₂O)₃]·H₂O}_n(1),{[Eu₂(L)₃(DMF)₂(H₂O)]·(H₂O)}_n(2){Tb₂(L)₃(DMF)₂(H₂O)]·H₂O}n(3) were successfully synthesized from H₂L(N,N’-bis(4-carbozylbenzyl)aniline).Remarkably,compound 3 has extremely high sensitivity to 4-n...     

Hydroxyl-and-carboxyl ligand concatenating multi-lanthanide substituted tellurotungstates and electrochemical detection of noradrenaline

Developing and exploring organic–inorganic hybrid multi-lanthanide (Ln) implanted heteropolyoxometalates (HPOMs) has bloomed into an emerging research field. In this article, two neoteric d-gluconic acids (H₆GA) concatenating multi-Ln^III implanted heteropolytungstates K₁₄H₁₀[Ln₄(H₂O)₄W₆(H₂GA)₄O₁₂(B-α-TeW₉O₃₃)₄]·60H₂O (Ln = La³⁺ (1), Pr³⁺ (2)) were obtained in acidic aqueous system. Attractively, in the polyanion structure of 1 and 2, six W^VI and four Ln^III centers are connected by four flexible H₂GA^4? ligands via carboxyl and hydroxyl groups, resulting in the heterometallic [Ln₄(H₂O)₄W₆(H₂GA)₄O₁₂]⁸⁺ cluster and then the heterometallic cluster is surrounded by four [B-α-TeW₉O₃₃]^8– segments. Electrochemical measurements for the 1@CFMCN/GCE sensor (CFMCN = carboxyl-functionalized multiwalled carbon nanotube; GCE = glass carbon electrode) demonstrate that 1@CFMCN/GCE shows benign recognition response to detecting noradrenaline (NDA). This research expands the structural diversity of Ln-implanted HPOMs and presents an electrochemical platform of recognizing NDA in the field of biosensors.     

Synthesis of two lanthanide clusters LnIII4 (Gd4 and Dy4) with [2 × 2] square grid shape: Magnetocaloric effect and slow magnetic relaxation behaviors

Two isostructural tetranuclear lanthanide clusters named [Ln₄(L)₄(CH₃O)₄]·CH₃OH (Ln = Gd(III) for 1, Dy(III) for 2, H₂L = N′-(2-hydroxy-3-methoxybenzylidene)-6-(hydroxymethyl) picolinohydrazide) were successfully isolated by using a polydentate Schiff based ligand and Ln(III) nitrate salts. The structures of 1 and 2 were characterized by X-ray structural analyses, they are held by four double deprotonated ligands L²⁻. In them all the lanthanide ions are eight-coordinated and distributed over four vertices of a parallelogram, presenting a Ln₄ cluster with a strict [2 × 2] square grid pattern. The details of magnetic analysis show that 1 displays weak anti-ferromagnetic exchange between neighboring Gd(III) ions through carboxylate oxygen and methanol oxygen ligand atoms. Furthermore, 1 exhibits significant magnetocaloric effect with the maximum entropy change –ΔS_m value of 28.5 J/(kg·K) for ΔH = 7.0 T at 2.0 K. For compound 2, remarkable slow magnetic relaxation behaviors are observed in the presence of zero magnetic field with τ₀ = 1.02 × 10⁻⁶ s and energy barrier ΔE/k_B = 43.24 K.     

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.     

Synthesis and crystal structure of a 1D chainlike rare earth coordinated tungstogermenate： [（CH3）4N]1.50H3.50[Gd（GeW11O39）（H2O）2]·2.5H2O

A 1D zigzag polyoxometalate [(CH3)4N]1.50H3.50[Gd(GeW11O39)(H2O)2]·2.5H2O(1) was synthesized by reaction of the monova-cant polyanion [α-GeW11O39]8- with Gd3+ ions in aqueous solution and characterized by IR, UV spectra, ICP, and X-ray crystallography. X-ray single-crystal structural analysis indicated that the title compound crystallized in a monoclinic lattice, C2/c space group with α=2.8201(5), b=2.2885(3), c=2.4033(4) nm,β=123.875 (2)°, V=12.878(4) nm3, Z=8, R1=0.0623, wR2=0.1287. The solid-state structure of the title compound displayed an infinite one-dimensional arrangement built up of [α-GeW11O39]8- polyanions connected by GdⅢ cations.     

Energy transfer and luminescent properties of Tb3+ and Tb3+, Yb3+ doped CNGG phosphors

In this work,calcium niobium gallium garnet(Ca₃ Nb_1.6875Ga_3.1875O₁₂-CNGG) ceramic samples singledoped with Tb³⁺ and co-doped with Tb³⁺ and Yb³⁺ ions were sintered by the solid-state reaction method.The structural characterization of the samples was carried out by X-ray diffraction measurements.The optimal concentration of Tb³⁺ ions corresponding to the maximum luminescence in the green spectral range in CNGG:...     

EXAFS study of cation reordering in NaYF4：Yb3＋,Tb3＋ up-conversion luminescence materials

The NaYF4：yb3＋,Tb3＋ （Xyb： 0.20, XTb： 0.04） materials were prepared using the co-precipitation method, lne as-preparea material was washed either with or without water in addition to ethanol and thereafter annealed for 5 h at 500℃. This resulted in materials with moderate or very high up-conversion luminescence intensity, respectively. The structural study carried out with X-ray powder diffraction revealed microstrains in the rare earth （R） sublattice that were relaxed for the material with very high up-conversion intensity thus decreasing energy losses. The local structural details were investigated with R LⅢ and Y K edge ex- tended X-ray absorption fine structure （EXAFS） using synchrotron radiation. Around 10 tool.% of the Yb3＋ ions were found to occupy the Na site in the material with very high up-conversion intensity. These Yb species formed clusters with the Tb3＋ ions occupying the regular Na/R sites. Such clustering enhanced the energy transfer between Yb3＋ and Tb3＋ thus intensifying the up-conversion emission.     

Steric hindrance effect of Schiff-base ligands on magnetic relaxation dynamics and emissive behavior of two dinuclear dysprosium complexes

The self-assembly reactions between mixed-ligand and tetrahydrate dysprosium acetate in the presence of mixed organic solvents lead to two structural similar dinuclear dysprosium complexes with composition formulas of Dy₂(L₁)₂(L₂)₂(CH₃OH)₂·CH₂Cl₂·CH₃OH(1) and Dy₂(L₁)₂(L₃)₂(CH₃OH)₂·CH₃CN(2),where L     

A novel fluorescent sensor for Al~(3+) and Zn~(2+) based on a new europium complex with a 1,10-phenanthroline ligand

A new europium complex Eu(tta)₃Li(la)based on 1,10-phenanthroline derivative(Li=(2-(3,5-dimethoxyphenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline),tta=2-thenoyItrifluoroacetone)was designed and synthesized.Its structure was characterized by¹H and¹³C NMR,elemental analysis,UV-vis,fluorescence spectra and single crystal X-ray diffraction.The crystal of the complex la belongs to monoclinic system with the space group P2_1/n.The europium complex la in the solid and in the solution displays the typical emission of Eu(III)ion centered at 612 nm as a result of the electric dipole transition(⁵D₀-?⁷F₂).It exhibits high quantum yield(20.42%),long lifetime(0.29 ms)and good CIE color coordinate(0.67,0.33)in solid.In addition,the complex shows high sensitivity and selectivity towards Al³⁺and Zn²⁺in methanol solution which can be attributed to the Al³⁺/Zn²⁺cation instead of Eu³⁺in the complex la.The LODs for Al³⁺and Zn²⁺were calculated to be 5.880×10^-7and 7.678×10^-8mol/L,respectively.Besides,the additions of Al³⁺and Zn²⁺express remarkable color changes from red to bright blue and ivory that can be clearly observed by the naked eye respectively.     

Synthesis,fluorescence properties of Tb(III) complexes with novel mono-substituted β-diketone ligands

Two novel pyridine-2,6-dicarboxylic acid derivatives of mono-β-diketone named methyl 6-biphenylacetyl-2-pyridinecarboxylate (MBP) and 6-biphenylacetyl-2-pyridinecarboxylic acid (BAA) and their corresponding binary complexes Tb(MBP)₃.6H₂O and Tb(BAA)₃·6H₂O were synthesized. The ligands were characterized by elemental analysis, FT-IR and ¹H-NMR, and the complexes were characterized with elemental analysis, FT-IR, ¹H-NMR and thermogravimetric and differential thermal analysis(TG-DTA). The investigation of fluorescence properties of the complexes Tb(MBP)₃·6H₂O and Tb(BAA)₃·6H₂O showed that the introduction of the biphenyl enlarged the π-conjugated system of the ligands and enhanced the luminescent intensity of the complexes. The Tb(III) ion could be sensitized more efficiently by the ligands, in particular, the fluorescence intensity of the complex Tb(BAA)₃·6H₂O was about 20% higher than that of Tb(MBP)₃·6H₂O and 30% higher than that of Tb(III) complexes with bis-β-diketone-type ligands that we have previously reported.     

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     

Two temperature-dependent 2D heterometallic Cd(II)–Dy(III) coordination polymers exhibiting slow magnetic relaxation and luminescence properties

Two unique two-dimensional (2D) Cd(II)–Dy(III) heterometallic coordination polymers, {[DyCd(HPMA)(PMA)₂(H₂O)₄]·2H₂O}_n (1) and [DyCd(PAA)(PMA)₂(H₂O)₃]_n (2, PAA^– = phenylacetate), were prepared successfully based on the phenylmalonic acid (H₂PMA). The construction of two polymers is sensitive to the reaction temperature and can be synthesized directionally at room temperature and 90 °C, respectively. Complexes 1 and 2 display 2D layer structures that include dinuclear [Dy₂] cluster node and Dy(III)-based 1D zigzag chain motif severally. The Dy(III)-based units in two structures both are spaced well with the adjacent ones by the diamagnetic Cd(II)-based moieties. The magnetic studies reveal that 1 and 2 both display slow magnetic relaxation with temperature-dependent relaxation peaks producing an effective energy barrier (Δτ) of 74.5 and 32.1 K, separately. Furthermore, the solid-state photophysical properties of 1 and 2 show strong characteristic luminescent emissions of Dy(III) ion in the visible region.