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     

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.     

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.     

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.     

Crystal structures and fluorescence properties of lanthanide complexes prepared with 2,2’-biphenyldicarboxylic acid and 2,2’：6’,2’’-terpyridine

Five lanthanide complexes of Ln₂(dpdc)₂(tpy)₂(NO₃)₂(H₂O)₂ [Ln=La (1), Ce (2), Pr (3), Sm (4), Gd (5), H₂dpdc=2,2’-biphenyldicarboxylic acid and tpy=2,2′:6′,2″-terpyridine] were prepared at room temperature and characterized by X-ray diffraction, FT-IR and thermo-gravimetric analysis. The results showed that complexes 1–5 were isostructural and consisted of dinuclear units [Ln₂(dpdc)₂(tpy)₂(NO₃)(H₂O)₂] bridged by two dpdc^2? ligands. The dinuclear units with strong intramolecular hydrogen bonds were assembled into 2D supramolecular layers by the weak π^…π staking interactions between pyridine rings of tpy. The TG analysis showed that the complexes 1–5 behaved higher thermal stability with no mass loss at < 320 °C. The lanthanide contraction effect and the solid state luminescence properties of complexes 1–5 were also investigated. The luminescence emission spectra of complexes 1–5 exhibited ligands emission bands and complex 3 and 4 had no typical emission in the visible region.     

Synthesis, Characterization, and Reactivity of Amine Bis（phenolato） Cyclopentadienyl Lanthanide Complexes

（C5H5）3Ln（THF）reacted with amine bis（phenol） LH2 [ L = Me2NCH2CH2N {CH2-（2-O-C6H2-But^1-3-Me- 5）}2 ] in a 1：1 molar ratio in THF to generate the amine bis（phenolato） cyclopentadienyl lanthanide complexes LLn（C5H5） （THF）·（THF）,（Ln = La （1）, n =0; Ln = Sm（2）, n = 1） in high yields. Complexes 1 and 2 were fully characterized by elemental analysis, NMR （for 1） and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P21/c space goup, a= 1.1595（1） nm, b = 1.8588（2） nm, c = 1.6647（1） nm, β = 98.490（2）°, V =3.5486（5） nm^3, Z =4, Dc = 1.338 mg· m^3,μ = 1240 mm^-1, F（000）= 1488, R =0.0249, wR = 0.0568. The crystal data of complex 2 are monoclinic, P21/c sp ace goup, a = 0.9692 （1） nm, b = 1.4583 （2） nm, c = 2.8192 （3） nm, = 96.805 （2）°, V = 3.9584 （7） nm^3, Z=4, Dc =1.340 mg · ma, μ = 1.524 mm^-1, F（000）= 1668, R =0.0346, wR =0.0756. The attempts failed to synthesize the amine bis（phenolate） lanthanide alkoxides by the reactions of complexes 1 and 2 with alcohols. The preliminary results revealed that complex 1 can initiate ε-caprolactone polymerization.     

Tetranuclear yttrium and gadolinium 2-acetylcyclopentanoate clusters: Synthesis and their use as spin-coating precursors for metal oxide film formation for field-effect transistor fabrication

Lanthanide clusters [Ln_4(μ_3-OH)_2(η~2-accp)_4((μ-O)-η~2-accp)_6](Ln = Y(4),Gd(5); accp = 2-acetylcyclopentanoate) are accessible by treatment of [M(NO_3)_3·6 H_2 O](M = Y(1),Gd(2)) with 3 equiv. of Haccp(3) in presence of NaOH. The molecular structures of 4 and 5 in the solid-state are discussed. The thermal behavior of 4 and 5 was studied by TG under Ar and O_2, showing multistep decomposition processes. Additionally, DSC studies were carried out under an atmosphere of O_2. PXRD measurements of the TG residues confirm the formation of Ln_2 O_3.Spin-coating experiments were carried out with 4 and 5 for Ln_2 O_3 film deposition on silicon substrates. The layers are smooth, close and are of thicknesses of 18.87±1.13 nm and 25.59 ± 4.55 nm for Ln = Y and Gd, which was evidenced by SEM and EDX studies. Field-effect transistors were successfully fabricated by deposition of carbon nanotubes on top of the Y_2 O_3 films and formation of palladium contacts by a lift-off procedure. An on/off ratio of more than 4 orders of magnitude is achieved without considerable leakage currents. These results demonstrate the potential use of spin-coated Y_2 O_3 as a gate dielectric in electronic devices.     

Slow magnetic relaxation in a 3D dysprosium(III)-fluoro-oxalate framework containing zig-zag [Dy–F]n chains

Dysprosium complexes based on [F–Dy] or near-linear [F–Dy–F] unit are of great concern in the field of single-molecule magnets due to their large magnetic anisotropy. Here, the crystal structure and the magnetic relaxation dynamics were reported for a three-dimensional (3D) metal–organic framework (MOF): [DyF(C₂O₄)(H₂O)₂]_n·2nH₂O (1), which is the unique MOF containing zig-zag [Dy–F]_n chains. Magnetic susceptibility characterization reveals that 1 is one of the few 3D MOFs which show slow magnetic relaxation under zero dc field. And the effective energy barrier of 72 K for 1 is also higher than most Dy-based 3D MOFs. The diamagnetic ion dilution study shows that the ferromagnetic exchange couplings mainly transmitted by F^? bridges in 1 contribute little to the energy barrier, but effectively suppress the quantum tunneling process and result in a smooth hysteresis loop with no waist-restricted step.     

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 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.     

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 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.     

Synthesis and Crystal Structure of A Bimetallic Terbium Complex Tb2 {μ-CH2 SiMe2 NC6 H3 ^iPr2 -2, 6}3 （THF）3

The reaction of 2, 6-^iPr2CbH3NHSiMe3 with Tb（CH2SiMe3）3（THF）2 in benzene at room temperature afforded a binuclear terbium complex Tb2 {μ-CH2 SiMe2 NC6 H3 ^iPr2 -2, 6}3（THF）3. X-ray diffraction revealed that Tb atoms were bridged by three methylene units. One Tb atom was six-coordinated by two nitrogen atoms, three methylene carbons, and one THF molecule, while the other Tb atom was six-coordinated by one nitrogen atom, three methylene carbons, and two THF molecules. Both Tb atoms adopted a distorted trigonal prism geometry.     

Synthesis and crystal structure of [Y(C_5Me_4SiMe_3){μ-O(CH_2)_3CH_3}{N(SiHMe_2)_2}]_2

A dimeric yttrium complex [Y(C5Me4SiMe3){μ-O(CH2)3CH3}{N(SiHMe2)2}]2 (1) was isolated as one of the byproducts from the reaction of Y{N(SiHMe2)3}3(THF)2 with C5Me4HSiMe3 in 1:1.1 molar ratio in toluene at 100 C for 2 d.Complex 1 was characterized by elemental analysis,NMR spectroscopy,FT-IR spectroscopy,and X-ray single crystal structure analysis.X-ray diffractions revealed that com-plex 1 was a symmetric dimer,and the center metal Y3+ was six-coordinated by one nitrogen atom from the amide group,two bridgi...     

Novel lanthanide coordination polymers based on mixed N,O-donor ligands and their visible-light-driven photocatalytic performance

In the present work,we prepared three isostructural lanthanide(Ln) coordination polymers(CPs).namely [Ln(Hhpc)(phen)(NO₃)](Ln=Gd(1),La(2),Y(3),H₃ hpc=5-hydroxy-1 H-pyrazole-3-carboxyIic acid,phen=1,10-phenanthroline) by hydrothermal method.Their structures were characterized by single crystal X-ray diffraction,Fourier transform infrared spectrum,elemental analysis,powder X-ray diffraction and thermal gravimetric analysis.CPs 1-3 are isostrutural and exhibit two-dimensional(...     

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.     

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.     

Synthesis and characterization of Co_(1-2x)Ni_xMn_xCe_yFe_(2-y)O_4 nanoparticles

Spinel ferrite Co_(1-2 x)Ni_xMn_xFe_(2-y)Ce_yO_4(0.0≤x=y≤0.3) nanoparticles(NPs) were prepared by sol-gel auto-combustion method.The synthesized NPs were examined using several techniques such as X-ray diffraction(XRD),field emission scanning electron microscopy(FE-SEM) coupled with EDX and elemental mapping,transmission electron microscopy(TEM),Fourier-transform infrared spectroscopy(FT-IR),and a vibrating sample magnetometer(VSM).The analysis of the crystal structure and the phase identification of samples indicates the formation of spinel cubic phase with the occurrence of CeO_2 as secondary phase when the content of Ce substitution element increases.In addition,all produced samples exhibit cubic symmetry with space group Fd3m.TEM confirms the presence of two phases,i.e.,the cubic spinel ferrite and the cubic cerium oxide(CeO_2).The characteristics of hysteresis loops reveal the soft ferrimagnetic nature of the different synthesized samples.The saturation(M_s) and remanent(M_r) magnetizations fall on increasing the content of substituting elements.Compared with pure CoFe_2O_4 NPs,the value of coercive field(H_c) slightly increases for x=y=0.1 and x=y=0,2 NPs.Then,H_c reduces with further increasing the x and y contents.The squareness ratio is found to be in the 0.528-0.400 interval,indicating the single domain NPs with uniaxial anisotropy for the different produced NPs.The magneto crystalline anisotropy constant(K_(eff)),anisotropy field(H_a),magneton number(n_B) and the demagnetizing field(N) were also determined and discussed.     

Alternating copolymerization of CO2 and cyclohexene oxide initiated by rare-earth metal complexes stabilized by o-phenylenediamine-bridged tris(phenolate) ligand

A series of o-phenylenediamine bridged tris(phenolate) ligand-stabilized rare-earth metal complexes were synthesized and characterized.Lanthanum(complex 1),neodymium(complex 2^tBu),and yttrium(complex 3) complexes stabilized by ligand of buiky tert-butyl substituents are mononuclear,whereas neodymium complexes 2^Me and 2^C1 bearing smaller methyl and chloro substituents are dinuclear,respectively.They were applied in the alternating copolymerization of CO₂     

Synthesis and Characterization of A Polynuclear Yttrium Trifluoroethoxide and Its Activity for Oligomerization of Phenyl Isocyanate

A polynuclear yttrium trifluoroethoxide was synthesized and its activity for the oligomerization of phenyl isocyanate was tested. Reaction of anhydrous YCl3 with CF3CH2ONa in a 1:3 molar ratio in THF at room temperature, after workup, gave complex 1 as colorless crystals. The composition of complex 1 is [Y(OCH2CF3)3]6ONa2(THF)12, which was identified by elemental analysis and 1H NMR. Further X-ray structure determination reveals that complex 1 is a polynuclear ion pair compound, [Y6(μ6-O)(OCH2CF3)18]2-[Na(THF)6] 2 (1). The crystal data of complex 1 are trigonal, P-3 space group, a=1.78440(14) nm, b=1.78440(14) nm, c=1.27395(12) nm, γ=120°, V=3.5129(5) nm3, Z=1, Dc=1.607 mg·m-3, μ=2.591 mm-1 (Mo Kα), F(000)=1710, R=0.067, wR=0.182. Preliminary results demonstrated that complex 1 is a highly effective catalyst for the oligomerization of phenyl isocyanate.