Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6...Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6',2″-terpyridine,were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4-OH-terpy.During the synthesis,4-OH-terpy was involved in the reaction as a neutral ligand,while HBA,in its deprotonated form(BA-),coordinated with the lanthanide ions as an acidic ligand.The crystal structures of these two complexes were precisely determined by single-crystal X-ray diffraction.Elemental analysis,infrared and Raman spectroscopy,and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes.The single-crystal X-ray diffraction data indicate that,despite their structural differences,both complexes belong to the triclinic crystal system P1 space group.The central lanthanide ions have the same coordination number but exhibit different coordination environments.To comprehensively evaluate the thermal stability of these two complexes,comprehensive tests including thermogravimetric analysis,differential thermogravimetric analysis,differential scanning calorimetry,Fourier transform infrared spectroscopy,and mass spectrometry were conducted.Meanwhile,an in-depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes.In addition,studies of the fluorescence properties of complex1 showed that it exhibited fluorescence emission matching the Sm^(3+)characteristic transition.展开更多
Two new dinuclear lanthanidecomplexes,namely[Ln_(2)(dbm)_(2)(HL)_(2)(CH_(3)OH)_(2)]·4CH_(3)OH[Ln=Tb(1)and Dy(2),Hdbm=dibenzoylmethane]have been synthesized using prepared multidentate Schiff base ligand H_(3)L(hy...Two new dinuclear lanthanidecomplexes,namely[Ln_(2)(dbm)_(2)(HL)_(2)(CH_(3)OH)_(2)]·4CH_(3)OH[Ln=Tb(1)and Dy(2),Hdbm=dibenzoylmethane]have been synthesized using prepared multidentate Schiff base ligand H_(3)L(hydroxy‑acetic acid(4‑diethylamino‑2‑hydroxy‑benzylidene)‑hydrazide)with good biological activity.Structure characterizations show that the complex comprises two Ln3+ions,two dbm-ions,two HL^(2-)ligands,two CH_(3)OH molecules,and four free methanol molecules.Each Ln^(3+)ion is eight‑coordinated.The two central Lnions are bridged by twoμ_(2)‑O atoms leading to a parallelogram[Ln2O2]core.The interaction between the compounds(H_(3)L,1,and 2)and the calf thymus DNA(CT‑DNA)has been further confirmed by UV‑Vis spectrometry,fluorescence titration,and cyclic voltammetry.The results showed that both 1 and 2 could undergo insertion with CT‑DNA.CCDC:2343005,1;2343006,2.展开更多
The complexes of rare earth elements with 1,2-diphenyl-4-butyl-3,5-Pyrazolidinedione （PBH, phenylbutazone） were synthesized and characterized by elemental analysis, molar conductance, IR, UV-Vis, EPR and magnetic mo...The complexes of rare earth elements with 1,2-diphenyl-4-butyl-3,5-Pyrazolidinedione （PBH, phenylbutazone） were synthesized and characterized by elemental analysis, molar conductance, IR, UV-Vis, EPR and magnetic moment measurements. Based on these studies the complexes were formulated as [Ln（PB）3（H2O）2].nH2O, where Ln=Eu（III）, Gd（III）, Tb（III）, Dy（III） and Er（III）. From IR spectra, it was found that PBH acted as a bidentate mono-ionic ligand coordinating through two carbonyl oxygen of the pyrazolidinedione ring. The thermal analysis of all the complexes was carried out at a heating rate of 10 oC/min. The kinetic aspects of the complexes were evaluated. The nega-tive entropy value of the complexes indicated a more ordered state for the activated complexes. The photoluminescence property of Tb（III） complex was investigated. It showed all the characteristic emission peaks of Tb^3＋ with a life time of 0.98914 ms.展开更多
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 design...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,CHO_(2)=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 Fe^(2+)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.展开更多
Lanthanide complexes of Eu（III）, Gd（III）, Nd（III）, Sm（III）, and Tb（III） with phenylthioacetic acid were synthesized and characterized by elemental analysis, mass, infrared radiation （IR）, electronic spectr...Lanthanide complexes of Eu（III）, Gd（III）, Nd（III）, Sm（III）, and Tb（III） with phenylthioacetic acid were synthesized and characterized by elemental analysis, mass, infrared radiation （IR）, electronic spectra, molar conductance, thermogravimetric analysis （TGA）, and powder X-ray diffraction （XRD）. The results showed that the lanthanide complexes were homodinuclear in nature. The two lanthanide ions were bridged by eight oxygen atoms from four carboxylate groups. Thermal decomposition profiles were consis- tent with the proposed formulations. Powder XRD studies showed that all the complexes were amorphous in nature. Antimicrobial studies indicated that these complexes exhibited more activity than the ligand itself. The DNA cleavage activity of the ligand and its complexes were assayed on CT DNA using gel electrophoresis in the presence of H202. The result showed that the Eu（Ⅲ） and Nd（Ⅲ） complexes completely cleaved the DNA. The anticancer activities of the complexes were also studied towards human cervical cancer cell line （HeLa） and colon cancer cells （HCT116） and it was found that the Eu（Ⅲ） and Nd（Ⅲ） complexes were more active than the corresponding Gd（Ⅲ）, Sm（Ⅲ）, Tb（Ⅲ） complexes and the free ligand on both the cancer cells.展开更多
Four ternary lanthanide complexes with unsaturated acid and 1,10-phenanthroline are prepared in methanol and characterized by elemental analysis, molar conductance, UV, IR, (()~1H) NMR and XPS. The results from this p...Four ternary lanthanide complexes with unsaturated acid and 1,10-phenanthroline are prepared in methanol and characterized by elemental analysis, molar conductance, UV, IR, (()~1H) NMR and XPS. The results from this paper show that the complexes Ln(phen)(SA)_3·2H_2O or Ln(phen)(CA)_3·H_2O (Ln=Ce(Ⅲ), Sm(Ⅲ) and Eu(Ⅲ), (phen=1,10-)phenanthroline, SA=Sorbate and CA=Cinnamate) has better anti-inflammatory effect than cerium nitrate and their gremores are steadier than cerium nitrate gremor. And there is a kind of medicament which can replace the cerium nitrate gremor completely in treating burn.展开更多
The two compounds of [Ln（2-FBA）3·2,2＇-bpy ]2（2-FBA = 2-fluorobenzoato, 2,2＇-bpy = 2,2＇-bipyridine, Ln = Eu（1 ）, Dy（2）） were synthesized and their structures were determined by X-ray diffraction method....The two compounds of [Ln（2-FBA）3·2,2＇-bpy ]2（2-FBA = 2-fluorobenzoato, 2,2＇-bpy = 2,2＇-bipyridine, Ln = Eu（1 ）, Dy（2）） were synthesized and their structures were determined by X-ray diffraction method. Crystallized complexes 1 and 2 are isomorphous, monoelinie system with P21/n space group. The two complexes are binuclear molecule with an inversion center. The two lanthanide ions are linked by four bridged 2-FBA ligands and each lanthanide ion is further bonded to one chelated bidentate 2-FBA ligand and one 2,2＇-bipyridine molecule. The coordination number of metal ion is eight. The europium complex exhibits strong red fluorescence. ^5D0→^7Fj（j = 1 - 4） transition emission of Eu^3＋ ion was observed.展开更多
The unique luminescent performance of lanthanide complexes/clay minerals hybrid materials has been fascinating many researchers for recent decades.It not only retains the excellent luminescent characteristics of lanth...The unique luminescent performance of lanthanide complexes/clay minerals hybrid materials has been fascinating many researchers for recent decades.It not only retains the excellent luminescent characteristics of lanthanide complexes but also improves the poor stability of the complexes.In this article,we introduce the luminescence mechanism of lanthanide complexes and point out the necessity of their combination with clay minerals.After the analysis of the structure and interlayer environment differences of 1:1-type and 2:1-type clay minerals,the intercalation methods(covalent grafting and ion exchange)appropriate for different clay minerals are summarized with examples.Based on the luminescence characteristics of the hybrid materials,the applications of these materials as luminescent probes in recognition of specific metal cations and molecules,detection of pH value,and temperature are reviewed.Finally,the current problems in the preparation of lanthanide complexes/clay minerals hybrid luminescent materials and shortcomings that need improvement in their performance are analyzed,and the application prospect is forecast.展开更多
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 roo...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 dpdc2？ 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.展开更多
Six genistein lanthanide complexes, LnL_2 (OAc)·nH_2O [Ln=La(Ⅲ), Sm(Ⅲ), Eu(Ⅲ), Gd(Ⅲ), (Tb(Ⅲ),) Dy(Ⅲ); L=genistein; n=4, 7, 8] were synthesized and characterized on the basis of elemental analyses, IR, (()~1...Six genistein lanthanide complexes, LnL_2 (OAc)·nH_2O [Ln=La(Ⅲ), Sm(Ⅲ), Eu(Ⅲ), Gd(Ⅲ), (Tb(Ⅲ),) Dy(Ⅲ); L=genistein; n=4, 7, 8] were synthesized and characterized on the basis of elemental analyses, IR, (()~1H) NMR spectra and molar conductivity. The scavenging activity of genistein and five lanthanides complexes on the hydroxyl free radicals (OH·) was also investigated by spectrophotometric methods. The results show that the scavenging activity of the complexes is better than that of the ligand and their scavenging ability can be assembled in the following order: Sm>La>Dy>Eu>Tb>L.展开更多
Four lanthanide coordination complexes, namely, [Ln（2,3-DClBA）3（5,5’-dmebipy）（H2O）]2（Ln=Sm（1）, Eu（2）, Dy（3）, Ho（4））; 2,3-DClBA=2,3-dichlorobenzoate; 5,5’-dmebipy=5,5’-dmethylbipyridine） were synthe...Four lanthanide coordination complexes, namely, [Ln（2,3-DClBA）3（5,5’-dmebipy）（H2O）]2（Ln=Sm（1）, Eu（2）, Dy（3）, Ho（4））; 2,3-DClBA=2,3-dichlorobenzoate; 5,5’-dmebipy=5,5’-dmethylbipyridine） were synthesized and characterized by elemental analysis, infrared spectroscopy and single crystal X-ray diffraction. Findings indicated that complex 3 was a dinuclear molecule, and the center Dy3＋ was eight-coordinated. Each dinuclear units could be connected by H bond and halogen-halogen interactions. Luminescent property of complex 2 suggested the typical intense emissions of Eu3＋ ions. Thermal analysis showed that the complexes decomposed in three steps： the coordination water was lost firstly then the neutral ligand 5,5’dmebipy was lost and lastly the 2,3-DClBA ligand was lost.展开更多
The lanthanide complexes containing a bulky tridentate [N,N,O] Schiff base ligand 3,5-But2-2-（OH）C6H2CH=N-8-C9H6N （HL） were synthesized and characterized. The reaction of anhydrous LnCl3 with NaL formed in situ in...The lanthanide complexes containing a bulky tridentate [N,N,O] Schiff base ligand 3,5-But2-2-（OH）C6H2CH=N-8-C9H6N （HL） were synthesized and characterized. The reaction of anhydrous LnCl3 with NaL formed in situ in a 1：1 molar ratio in THF at room temperature afforded the lanthanide Schiff base dichloride complexes LnLCl2（DME） （Ln=Eu （1）; Sm （2））. Complexes 1 and 2 can be used as precursors for the synthesis of the lanthanide cyclopentadienyl Schiff base derivatives. The reactions of complexes 1 and 2 with one equiv of NaCH3C5H4 in THF provided the desired products LnL（CH3C5H4）CI（THF）.THF （Ln=Eu （3）; Sm （4）） in good isolated yields. These complexes were characterized by elemental analysis, IR spectra, and X-ray structural determination, in the case of complexes 3 and 4. The crystal data of complex 3 are monoclinic, P21/C space group, a=1.3370（2） nm, b=1.5190（2） nm, c=1.8910（3） nm, β=109.846（4）°, V=3.6125（8） nm^3, Z=4, Dc=1.416 mg/m^3,μ=1.847 mm^-1, F（000）=1584, R=0.0707, wR=0.1350. The crystal data of complex 4 are monoclinic, P21/c space group, a=1.3383（1） nm, b=1.5210（2） nm, c=1.8960（2） nm, β =109.878（3）°, V=3.6293（7） nm^3, Z=4, Dc=1.407 mg/m^3, μ=1.728 mm^-1, F（000）= 1580, R=0.0670, wR=0.1385.展开更多
Supramolecular incorporation of lanthanide complex has been obtained by loading of organic ligand into Eu3+-exchanged zeolite L. This was achieved by a two-step procedure: (1) zeolite L was ion-exchanged with Eu(Ⅲ) i...Supramolecular incorporation of lanthanide complex has been obtained by loading of organic ligand into Eu3+-exchanged zeolite L. This was achieved by a two-step procedure: (1) zeolite L was ion-exchanged with Eu(Ⅲ) ions; (2) organic ligand was then loaded into the channels of the Eu3+-exchanged zeolite by gas diffusion procedure. Loading of ligand into the channels of zeolite L was confirmed by element analysis. Luminescence spectroscopy has confirmed that lanthanide complex are formed in the nanochannels of zeolite L crystals. In addition to the sharp emissions of lanthanide ions, broad band ranged from 350～500 nm can also be observed. This study provides alternative method for fabricating full-color display materials.展开更多
Several dinuclear lanthanide complexes of Ln2(HTH)6TPPHZ (Ln=Eu, Sm, Er, Nd, Yb, Ho; TPPHZ=Tetrapyrido (3,2-a:2’,3’-c:3’,2'-h:2'’,3’'-j) phenazine; HTH=4,5,5,6,6,6-heptafluroro-1-(2-thienyl)hexane-1,3...Several dinuclear lanthanide complexes of Ln2(HTH)6TPPHZ (Ln=Eu, Sm, Er, Nd, Yb, Ho; TPPHZ=Tetrapyrido (3,2-a:2’,3’-c:3’,2'-h:2'’,3’'-j) phenazine; HTH=4,5,5,6,6,6-heptafluroro-1-(2-thienyl)hexane-1,3-dione were synthesized and their photoluminescence properties were investigated. After ligand-mediated excitation, all the complexes showed the characteristic luminescence of the corresponding Ln(III) ions in the visible and NIR regions attributed to energy transfer from the ligands to the metal center. For Eu...展开更多
（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 LL...（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.展开更多
A novel lanthanide coordination polymer formulated as [Nd(dpdo) 4(H 2O) 3] 3·4.5H 2O·dpdo 1(dpdo=4,4′-dipyrazine-dioxide) was synthesized and structurally characterized. The Nd 3+ ions are bridged b...A novel lanthanide coordination polymer formulated as [Nd(dpdo) 4(H 2O) 3] 3·4.5H 2O·dpdo 1(dpdo=4,4′-dipyrazine-dioxide) was synthesized and structurally characterized. The Nd 3+ ions are bridged by dpdo ligands in a cis-mode to form a zigzag chain along direction. Meanwhile, each Nd 3+ ion is coordinated with three terminal dpdo molecules. One of them is overlapped with the bridging one through π-π stackings, and the other two are bound to the opposite directions of the bridging ones, producing a ribbon-like motif with rectangular cavity. These adjacent ribbons are connected through inter-molecular π-π stackings to give parquet-like architecture with a large rectangular channel (1.108 nm×1.660 nm) in which the crystal lattice water molecules and ClO 4 - anions are included. Thermal analysis shows that the solvate dpdo and water molecules can be removed at lower temperature, while coordinated dpdo molecules are lost simultaneously at higher temperature.展开更多
A series of novel rare earths complexes with Schiff base of pridoxylidence-glycine acid (HL) were synthesized in absolute methanol under argon atmosphere. The complexes were characterized by elemental analysis, molar ...A series of novel rare earths complexes with Schiff base of pridoxylidence-glycine acid (HL) were synthesized in absolute methanol under argon atmosphere. The complexes were characterized by elemental analysis, molar conductivity, IR, UV spectra, and H-NMR spectra et al. Data indicate that the complexes have a general formula Ln LCl2.3H(2)O (Ln = La, Y, Sm, Gd, Dy, Yb; L = C10H11N2O4). Effects of the complexes (Ln = La) on physiological and biochemical indexes of plants under Pb stress were studied. The experiments shown that the complexes obviously mitigated Pb pollution results in decreasing of chlorophyll content, rising of cell membrane permeability, changing catalase(CAT) and distribution of Pb.展开更多
By the reaction of Cp 3Ln with HL(Cp=η 5 C 5H 5, cyclopentadienyl; Ln=Yb, Tm, Er, Ho, Dy, Gd, Pr; HL=benzohydroximic acid), seven new complexes of the general formula Cp 2LnL were synthesized. All the complexes...By the reaction of Cp 3Ln with HL(Cp=η 5 C 5H 5, cyclopentadienyl; Ln=Yb, Tm, Er, Ho, Dy, Gd, Pr; HL=benzohydroximic acid), seven new complexes of the general formula Cp 2LnL were synthesized. All the complexes were characterized by elemental analysis, infrared spectra, and mass spectra. Based on these data, the probable structure was proposed.展开更多
The characteristics of styrene-acrylic acid copolymer supported lanthanide complexes (SAAC Ln) (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tin, Yb, and Lu) were described. A comparison of the activities of SAAC...The characteristics of styrene-acrylic acid copolymer supported lanthanide complexes (SAAC Ln) (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tin, Yb, and Lu) were described. A comparison of the activities of SAAC·Ln was made. It was found that in the polymerization of butadiene, a peak in activity appeared at Nd and Pr, Sin, Eu and the heavy lanthanides exhibited low or no activities. The effects of some factors on the activities were discussed. The microstructure of the polymers obtained with all the lanthanides in the series were the same and the content of cis-1, 4 polybutadiene attained was more than 98%.展开更多
A series of new complexes of formula Ln(acac)_s(Ph_3PO)_3 (where Ln^(3+)=Nd^(3+), Sm^(3+), Eu^(3+), Tb^(3+), Ho^(3+)) have been prepared and characterized. The coordination of two ligands with lanthanide ions are stud...A series of new complexes of formula Ln(acac)_s(Ph_3PO)_3 (where Ln^(3+)=Nd^(3+), Sm^(3+), Eu^(3+), Tb^(3+), Ho^(3+)) have been prepared and characterized. The coordination of two ligands with lanthanide ions are studied by IR spectra, ~1H, ^(13)C, ^(31)P-NMR and metal-ligand charge tranafer tranaition is also discussed via electronic adaorption and luminescence spectroscopy.展开更多
文摘Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6',2″-terpyridine,were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4-OH-terpy.During the synthesis,4-OH-terpy was involved in the reaction as a neutral ligand,while HBA,in its deprotonated form(BA-),coordinated with the lanthanide ions as an acidic ligand.The crystal structures of these two complexes were precisely determined by single-crystal X-ray diffraction.Elemental analysis,infrared and Raman spectroscopy,and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes.The single-crystal X-ray diffraction data indicate that,despite their structural differences,both complexes belong to the triclinic crystal system P1 space group.The central lanthanide ions have the same coordination number but exhibit different coordination environments.To comprehensively evaluate the thermal stability of these two complexes,comprehensive tests including thermogravimetric analysis,differential thermogravimetric analysis,differential scanning calorimetry,Fourier transform infrared spectroscopy,and mass spectrometry were conducted.Meanwhile,an in-depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes.In addition,studies of the fluorescence properties of complex1 showed that it exhibited fluorescence emission matching the Sm^(3+)characteristic transition.
文摘Two new dinuclear lanthanidecomplexes,namely[Ln_(2)(dbm)_(2)(HL)_(2)(CH_(3)OH)_(2)]·4CH_(3)OH[Ln=Tb(1)and Dy(2),Hdbm=dibenzoylmethane]have been synthesized using prepared multidentate Schiff base ligand H_(3)L(hydroxy‑acetic acid(4‑diethylamino‑2‑hydroxy‑benzylidene)‑hydrazide)with good biological activity.Structure characterizations show that the complex comprises two Ln3+ions,two dbm-ions,two HL^(2-)ligands,two CH_(3)OH molecules,and four free methanol molecules.Each Ln^(3+)ion is eight‑coordinated.The two central Lnions are bridged by twoμ_(2)‑O atoms leading to a parallelogram[Ln2O2]core.The interaction between the compounds(H_(3)L,1,and 2)and the calf thymus DNA(CT‑DNA)has been further confirmed by UV‑Vis spectrometry,fluorescence titration,and cyclic voltammetry.The results showed that both 1 and 2 could undergo insertion with CT‑DNA.CCDC:2343005,1;2343006,2.
基金support from the University of Kerala for the award of afellowship
文摘The complexes of rare earth elements with 1,2-diphenyl-4-butyl-3,5-Pyrazolidinedione （PBH, phenylbutazone） were synthesized and characterized by elemental analysis, molar conductance, IR, UV-Vis, EPR and magnetic moment measurements. Based on these studies the complexes were formulated as [Ln（PB）3（H2O）2].nH2O, where Ln=Eu（III）, Gd（III）, Tb（III）, Dy（III） and Er（III）. From IR spectra, it was found that PBH acted as a bidentate mono-ionic ligand coordinating through two carbonyl oxygen of the pyrazolidinedione ring. The thermal analysis of all the complexes was carried out at a heating rate of 10 oC/min. The kinetic aspects of the complexes were evaluated. The nega-tive entropy value of the complexes indicated a more ordered state for the activated complexes. The photoluminescence property of Tb（III） complex was investigated. It showed all the characteristic emission peaks of Tb^3＋ with a life time of 0.98914 ms.
基金supported by the National Natural Science Foundation of China (51962008)。
文摘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,CHO_(2)=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 Fe^(2+)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.
文摘Lanthanide complexes of Eu（III）, Gd（III）, Nd（III）, Sm（III）, and Tb（III） with phenylthioacetic acid were synthesized and characterized by elemental analysis, mass, infrared radiation （IR）, electronic spectra, molar conductance, thermogravimetric analysis （TGA）, and powder X-ray diffraction （XRD）. The results showed that the lanthanide complexes were homodinuclear in nature. The two lanthanide ions were bridged by eight oxygen atoms from four carboxylate groups. Thermal decomposition profiles were consis- tent with the proposed formulations. Powder XRD studies showed that all the complexes were amorphous in nature. Antimicrobial studies indicated that these complexes exhibited more activity than the ligand itself. The DNA cleavage activity of the ligand and its complexes were assayed on CT DNA using gel electrophoresis in the presence of H202. The result showed that the Eu（Ⅲ） and Nd（Ⅲ） complexes completely cleaved the DNA. The anticancer activities of the complexes were also studied towards human cervical cancer cell line （HeLa） and colon cancer cells （HCT116） and it was found that the Eu（Ⅲ） and Nd（Ⅲ） complexes were more active than the corresponding Gd（Ⅲ）, Sm（Ⅲ）, Tb（Ⅲ） complexes and the free ligand on both the cancer cells.
文摘Four ternary lanthanide complexes with unsaturated acid and 1,10-phenanthroline are prepared in methanol and characterized by elemental analysis, molar conductance, UV, IR, (()~1H) NMR and XPS. The results from this paper show that the complexes Ln(phen)(SA)_3·2H_2O or Ln(phen)(CA)_3·H_2O (Ln=Ce(Ⅲ), Sm(Ⅲ) and Eu(Ⅲ), (phen=1,10-)phenanthroline, SA=Sorbate and CA=Cinnamate) has better anti-inflammatory effect than cerium nitrate and their gremores are steadier than cerium nitrate gremor. And there is a kind of medicament which can replace the cerium nitrate gremor completely in treating burn.
文摘The two compounds of [Ln（2-FBA）3·2,2＇-bpy ]2（2-FBA = 2-fluorobenzoato, 2,2＇-bpy = 2,2＇-bipyridine, Ln = Eu（1 ）, Dy（2）） were synthesized and their structures were determined by X-ray diffraction method. Crystallized complexes 1 and 2 are isomorphous, monoelinie system with P21/n space group. The two complexes are binuclear molecule with an inversion center. The two lanthanide ions are linked by four bridged 2-FBA ligands and each lanthanide ion is further bonded to one chelated bidentate 2-FBA ligand and one 2,2＇-bipyridine molecule. The coordination number of metal ion is eight. The europium complex exhibits strong red fluorescence. ^5D0→^7Fj（j = 1 - 4） transition emission of Eu^3＋ ion was observed.
基金Project supported by the National Natural Science Foundation of China(51872269,42072053)。
文摘The unique luminescent performance of lanthanide complexes/clay minerals hybrid materials has been fascinating many researchers for recent decades.It not only retains the excellent luminescent characteristics of lanthanide complexes but also improves the poor stability of the complexes.In this article,we introduce the luminescence mechanism of lanthanide complexes and point out the necessity of their combination with clay minerals.After the analysis of the structure and interlayer environment differences of 1:1-type and 2:1-type clay minerals,the intercalation methods(covalent grafting and ion exchange)appropriate for different clay minerals are summarized with examples.Based on the luminescence characteristics of the hybrid materials,the applications of these materials as luminescent probes in recognition of specific metal cations and molecules,detection of pH value,and temperature are reviewed.Finally,the current problems in the preparation of lanthanide complexes/clay minerals hybrid luminescent materials and shortcomings that need improvement in their performance are analyzed,and the application prospect is forecast.
基金Project supported by National Basic Research Program of China(2010CB732300)Foundation of Zhejiang Province Education Commission of China(Y201224213)
文摘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 dpdc2？ 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.
文摘Six genistein lanthanide complexes, LnL_2 (OAc)·nH_2O [Ln=La(Ⅲ), Sm(Ⅲ), Eu(Ⅲ), Gd(Ⅲ), (Tb(Ⅲ),) Dy(Ⅲ); L=genistein; n=4, 7, 8] were synthesized and characterized on the basis of elemental analyses, IR, (()~1H) NMR spectra and molar conductivity. The scavenging activity of genistein and five lanthanides complexes on the hydroxyl free radicals (OH·) was also investigated by spectrophotometric methods. The results show that the scavenging activity of the complexes is better than that of the ligand and their scavenging ability can be assembled in the following order: Sm>La>Dy>Eu>Tb>L.
基金supported by the National Natural Science Foundation of China(21073053,21473049)the Natural Science Foundation of Hebei Province,China(B2016205207)
文摘Four lanthanide coordination complexes, namely, [Ln（2,3-DClBA）3（5,5’-dmebipy）（H2O）]2（Ln=Sm（1）, Eu（2）, Dy（3）, Ho（4））; 2,3-DClBA=2,3-dichlorobenzoate; 5,5’-dmebipy=5,5’-dmethylbipyridine） were synthesized and characterized by elemental analysis, infrared spectroscopy and single crystal X-ray diffraction. Findings indicated that complex 3 was a dinuclear molecule, and the center Dy3＋ was eight-coordinated. Each dinuclear units could be connected by H bond and halogen-halogen interactions. Luminescent property of complex 2 suggested the typical intense emissions of Eu3＋ ions. Thermal analysis showed that the complexes decomposed in three steps： the coordination water was lost firstly then the neutral ligand 5,5’dmebipy was lost and lastly the 2,3-DClBA ligand was lost.
基金the National Natural Science Foundation of Chinathe Natural Science Foundation of Jiangsu Province (BK2007505)Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions (07KJA15014)
文摘The lanthanide complexes containing a bulky tridentate [N,N,O] Schiff base ligand 3,5-But2-2-（OH）C6H2CH=N-8-C9H6N （HL） were synthesized and characterized. The reaction of anhydrous LnCl3 with NaL formed in situ in a 1：1 molar ratio in THF at room temperature afforded the lanthanide Schiff base dichloride complexes LnLCl2（DME） （Ln=Eu （1）; Sm （2））. Complexes 1 and 2 can be used as precursors for the synthesis of the lanthanide cyclopentadienyl Schiff base derivatives. The reactions of complexes 1 and 2 with one equiv of NaCH3C5H4 in THF provided the desired products LnL（CH3C5H4）CI（THF）.THF （Ln=Eu （3）; Sm （4）） in good isolated yields. These complexes were characterized by elemental analysis, IR spectra, and X-ray structural determination, in the case of complexes 3 and 4. The crystal data of complex 3 are monoclinic, P21/C space group, a=1.3370（2） nm, b=1.5190（2） nm, c=1.8910（3） nm, β=109.846（4）°, V=3.6125（8） nm^3, Z=4, Dc=1.416 mg/m^3,μ=1.847 mm^-1, F（000）=1584, R=0.0707, wR=0.1350. The crystal data of complex 4 are monoclinic, P21/c space group, a=1.3383（1） nm, b=1.5210（2） nm, c=1.8960（2） nm, β =109.878（3）°, V=3.6293（7） nm^3, Z=4, Dc=1.407 mg/m^3, μ=1.728 mm^-1, F（000）= 1580, R=0.0670, wR=0.1385.
文摘Supramolecular incorporation of lanthanide complex has been obtained by loading of organic ligand into Eu3+-exchanged zeolite L. This was achieved by a two-step procedure: (1) zeolite L was ion-exchanged with Eu(Ⅲ) ions; (2) organic ligand was then loaded into the channels of the Eu3+-exchanged zeolite by gas diffusion procedure. Loading of ligand into the channels of zeolite L was confirmed by element analysis. Luminescence spectroscopy has confirmed that lanthanide complex are formed in the nanochannels of zeolite L crystals. In addition to the sharp emissions of lanthanide ions, broad band ranged from 350～500 nm can also be observed. This study provides alternative method for fabricating full-color display materials.
基金Project supported by the National Natural Science Foundation of China (20701019, 20971067, 20721002)the Natural Science Foundation of Ji-angsu Province (BK2008257)the Major State Basic Research Development Program (2006CB806104, 2007CB925103)
文摘Several dinuclear lanthanide complexes of Ln2(HTH)6TPPHZ (Ln=Eu, Sm, Er, Nd, Yb, Ho; TPPHZ=Tetrapyrido (3,2-a:2’,3’-c:3’,2'-h:2'’,3’'-j) phenazine; HTH=4,5,5,6,6,6-heptafluroro-1-(2-thienyl)hexane-1,3-dione were synthesized and their photoluminescence properties were investigated. After ligand-mediated excitation, all the complexes showed the characteristic luminescence of the corresponding Ln(III) ions in the visible and NIR regions attributed to energy transfer from the ligands to the metal center. For Eu...
基金Project supported by the National Natural Science Foundation of China (20472063)the Key Laboratory of Organic Synthesis of Jiangsu Province
文摘（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.
文摘A novel lanthanide coordination polymer formulated as [Nd(dpdo) 4(H 2O) 3] 3·4.5H 2O·dpdo 1(dpdo=4,4′-dipyrazine-dioxide) was synthesized and structurally characterized. The Nd 3+ ions are bridged by dpdo ligands in a cis-mode to form a zigzag chain along direction. Meanwhile, each Nd 3+ ion is coordinated with three terminal dpdo molecules. One of them is overlapped with the bridging one through π-π stackings, and the other two are bound to the opposite directions of the bridging ones, producing a ribbon-like motif with rectangular cavity. These adjacent ribbons are connected through inter-molecular π-π stackings to give parquet-like architecture with a large rectangular channel (1.108 nm×1.660 nm) in which the crystal lattice water molecules and ClO 4 - anions are included. Thermal analysis shows that the solvate dpdo and water molecules can be removed at lower temperature, while coordinated dpdo molecules are lost simultaneously at higher temperature.
文摘A series of novel rare earths complexes with Schiff base of pridoxylidence-glycine acid (HL) were synthesized in absolute methanol under argon atmosphere. The complexes were characterized by elemental analysis, molar conductivity, IR, UV spectra, and H-NMR spectra et al. Data indicate that the complexes have a general formula Ln LCl2.3H(2)O (Ln = La, Y, Sm, Gd, Dy, Yb; L = C10H11N2O4). Effects of the complexes (Ln = La) on physiological and biochemical indexes of plants under Pb stress were studied. The experiments shown that the complexes obviously mitigated Pb pollution results in decreasing of chlorophyll content, rising of cell membrane permeability, changing catalase(CAT) and distribution of Pb.
文摘By the reaction of Cp 3Ln with HL(Cp=η 5 C 5H 5, cyclopentadienyl; Ln=Yb, Tm, Er, Ho, Dy, Gd, Pr; HL=benzohydroximic acid), seven new complexes of the general formula Cp 2LnL were synthesized. All the complexes were characterized by elemental analysis, infrared spectra, and mass spectra. Based on these data, the probable structure was proposed.
文摘The characteristics of styrene-acrylic acid copolymer supported lanthanide complexes (SAAC Ln) (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tin, Yb, and Lu) were described. A comparison of the activities of SAAC·Ln was made. It was found that in the polymerization of butadiene, a peak in activity appeared at Nd and Pr, Sin, Eu and the heavy lanthanides exhibited low or no activities. The effects of some factors on the activities were discussed. The microstructure of the polymers obtained with all the lanthanides in the series were the same and the content of cis-1, 4 polybutadiene attained was more than 98%.
文摘A series of new complexes of formula Ln(acac)_s(Ph_3PO)_3 (where Ln^(3+)=Nd^(3+), Sm^(3+), Eu^(3+), Tb^(3+), Ho^(3+)) have been prepared and characterized. The coordination of two ligands with lanthanide ions are studied by IR spectra, ~1H, ^(13)C, ^(31)P-NMR and metal-ligand charge tranafer tranaition is also discussed via electronic adaorption and luminescence spectroscopy.
