Synthesis and Fluorescent and Magnetic Properties of a New Europium Complex Eu(C_(20)H_(14)O_3N)_3(2,2'-bipy)(H_2O)·H_2O

A new europium(Ⅲ) complex Eu(C_(20)H_(14)O_3N)_3(2,2?-bipy)(H_2O)·H_2O has been synthesized with2-diphenylanine carbonyl benzoic acid and 2,2?-bipyridine as ligands.Crystal data for the complex are as follows:triclinic,space group ■,a=11.3334(5),b=16.0883(7),c=17.0116(8)?,α=70.411(4)o,β=82.435(4)o,γ=85.095(4)o,V=2894.0(2)?~3,D_c=1.484 g/cm~3,Z=2,μ=1.15 mm~(-1),F(000)=1320 and the final R=0.0447 and w R=0.0578.The Eu(Ⅲ) ion is coordinated by nine atoms to give a monocapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu~(3+):~5D_0→~7F_1 (592 nm) and ~5D_0→~7F_2 (616 nm),respectively.Also reported is the magnetic property of the complex.The complex exhibits antiferromagnetism in the temperature range of 300～2 K.     

Synthesis and the Fluorescent,Magnetic and Thermal Stability Properties of a New Terbium(Ⅲ) Complex Tb(C_(20)H_(14)O_3N)_3(C_(12)H_8N_2)(H_2O)·H_2O

A new terbium(Ⅲ complex Tb(C_(20)H_(14)O_3N)_3(C_(12)H_8N_2)(H_2O)·H_2O has been synthesized with 2-diphenylanine carbonyl benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: triclinic, space group P1, a =11.6034(6), b = 16.2465(8), c = 16.4427(8) ?, α = 73.168(5)o, β = 88.655(4)o, γ = 82.865(4)o, V = 2943.7(3) ?~3, Dc = 1.494 g/cm~3, Z = 2, μ(MoK α) = 1.272 mm~(-1), F(000) = 1348, the final R = 0.0535 and w R = 0.0809. The Tb(Ⅲ) ion is coordinated by nine atoms to give a monocapped square antiprism coordination geometry. The complex shows four fluorescence emission bands arising from the transitions of Tb~(3+): ~5D_4 → ~7F_6(491 nm), ~5D_4 → ~7F_5(546 nm), ~5D_4 → ~7F_4(585 nm) and ~5D_4→~7F_3(621 nm). Also reported are the magnetic and thermal stability properties of the complex.     

Synthesis,Fluorescence and Magnetic Properties of a New Europium(Ⅲ) Complex Eu(C_(14)H_9O_3)_2(C_(12)H_8N_2)_2(NO_3)

A new europium(III)complex Eu(C_(14)H_9O_3)_2(C_(12)H_8N_2)_2(NO_3)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2_1/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D_c=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm~(-1),F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu~(3+):~5D_0→~7F_1(594 nm)and ~5D_0→~7F_2(618 nm).In addition,its X_(m )T decreases from 1.29767 cm~3?mol~(-1)?K at 300 K to 0.01531 cm~3?mol~(-1)?K at 2 K.     

Synthesis and Fluorescent,Magnetic and Thermal Stability Properties of a New Europium(Ⅲ) Complex Eu_2(C_(15)H_(11)O_3)_6(C_(12)H_8N_2)_2

A new europium(Ⅲ) complex Eu_2(C_(15)H_(11)O_3)_6(C_(12)H_8N_2)_2 has been synthesized with 2-(4-Methylbenzoyl)benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: monoclinic, space group P21/n, a = 15.1238(5), b = 13.5928(4), c = 22.9840(7) ?, β = 104.132(3)o, V = 4582.0(2) ?~3, D_c = 1.522 g/cm~3, Z = 4, μ(Mo Kα) = 1.433 mm~(-1), F(000) = 2128, the final R = 0.0447 and wR = 0.0826. The Eu(Ⅲ) ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry. The complex shows two intense fluorescence emission bands arising from the transitions of Eu3+: 5 D0 → 7 F1(594 nm) and 5 D0 → 7 F2(617 nm). The complex is an antiferromagnetism system in the range of 150～300 K. Also reported in the paper is the thermal stability property of the title complex.     

Synthesis,Fluorescence and Magnetic Properties of a New Europium(Ⅲ) Complex Eu(L)_3(Phen)_2

A new europium(III) complex Eu(L)3(Phen)2(1) with 2-benzoylbenzoic acid(HL) and 1,10-phenanthroline(Phen) as ligands has been synthesized. Crystal data for the complex are as follows: monoclinic, space group P21/c, a = 2.2577(4), b = 1.23484(19), c = 1.8789(3) nm, β = 94.918(3)o, V = 5.2189(14) nm~3, Dc = 1.512 g/cm~3, Z = 4, μ(Mo Kα) = 1.269 mm~(-1), F(000) = 2408, the final R = 0.0433 and w R = 0.1038. The Eu(III) ion is coordinated by nine atoms to give a single-capped square antiprism coordination geometry. 1 shows two intense fluorescence emission bands arising from the transitions of Eu~(3+): ~5D_0→~7F_1(597 nm) and ~5D_0→~7F_2(615 nm) with an excitation wavelength of 396 nm. In addition, 1 displays antiferromagnetic property at low temperature.     

Complexation of radionuclide ~(152+154)Eu(Ⅲ) with alumina-bound fulvic acid studied by batch and time-resolved laser fluorescence spectroscopy

To contribute to the understanding of Eu(Ⅲ)interaction properties on hydrous alumina particles in the absence and presence of fulvic acid(FA),the complexation properties of Eu(Ⅲ)with hydrous alumina,FA and FA-alumina hybrids are studied by batch and time-resolved laser fluorescence spectroscopy(TRLFS)techniques.The continuous increase in the fluorescence lifetime of Eu-alumina and Eu-FA with increasing pH indicates that the complexation is accompanied by decreasing number of hydration water in the first coordination sphere of Eu(Ⅲ).Eu(Ⅲ)is adsorbed onto alumina particles as outer-sphere surface complexes of≡(Al-O)-Eu·(OH)·7H_2O and≡(Al-O)-Eu·6H_2O at low pH values,and as inner-sphere surface complexes as≡(Al-O)_2-Eu~+·4H_2O at high pH.In FA solution,Eu(Ⅲ)forms complexes with FA as(COO)_2Eu~+(H_2O)_x and the hydration water number in the first coordination sphere decreases with pH increasing.The formation of≡COO-Eu-(O-Al≡)·4H_2O is observed on FA-alumina hybrids,suggesting the formation of strong inner-sphere surface complexes in the presence of FA.The surface complexes are also characterized by their emission spectra[the ratio of emission intensities of~5D_0→~7F_1(λ=594nm)and~5D_0→~7F_2(λ=619nm)transitions]and their fluorescence lifetime.The findings is important to understand the contribution of FA in the complexation properties of Eu(Ⅲ)on FA-alumina hybrids that the clarification of the environmental behavior of humic substances is necessary to understand fully the behavior of Eu(Ⅲ),or its analogue trivalent lanthanide and actinide ions in natural environment.     

CRYSTAL STRUCTURE OF A HETERONUCLEAR LANTHANIDE COMPLEX OF ERBIUM-YTTRIUM AND GLYCINE[ErY(GlY)_6(H_2O)_4](ClO_4)_65H_2O

The title complex [ErY(Gly)_6(H_2O)_4](ClO_4)_6 5H_2O has been synthesized.Its crystalstructure has been determined by X-ray diffraction method.The crystal is triclinic with space groupP1.The unit cell parameters are as follows:a=11.518(4),b=14.105(7),c=15.530(6) ,α=96.61(3),β=102.74(3),γ=105.70(3)°,V=2327.7(17) ~3,Z=2,Dc=2.091g/cm~3.The structure has been refinedto a final R of 0.0785.The crystal is an infinite chain complex,in which four carboxyl groups fromglycine molecules bridge the Er(Ⅲ)and Y(Ⅲ)ion,other two carboxyl groups bridge two adjacentEr(Ⅲ)or two Y(Ⅲ)ions.     

MOLYBDENUM-IRON MIXED METAL CLUSTERS (Ⅰ)——THE SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF (η~5-C_5H_5)_2Mo_2Fe_2(μ_4-Te)(μ_3-Te)_2(CO)_6

The reaction of Fe_2(μ_3-Te)_2(CO)_9 with Mo_2(CO)_6(η~5-C_5H_5) affords the title compound. Its X-ray analysis shows a butterfly structure for the Mo_2Fe_2 core; the two molybdenum atoms occupy the hinge with a Mo—Mo bond distance of 2.819 and the two iron atoms are on the tops of the wings with an average Mo—Fe bond distance of 2.932(2). Each molybdenum is bonded to a Cp ring, and three CO ligands are terminally bonded to each iron atom. One tellurium atom quadruply bridges Mo_Fe_2 with Mo—Te(μ_4)=2.625(2). and Fe—Te(μ_4)=2.713(2). Two tellurium atoms triply bridge the two triangular Mo_2Fe faces with Mo—Te(μ_3)=2.678(1) and Fe—Te(μ_3)=2.513(3). The molecule has C_(2v) symmetry and a bicapped triangle bipyramidal skeleton. Crystallographic parameters are as follows: space groupImm2(orthorhombic), a=14.562(3), b=10.391(1), c=7.139(4), V=1080.2(i)~3, Z=2, ρ(cald)=1.819g·cm~(-3). The final R factor was 2.2％ for 620 independent reflections(I>2σ(I)).     

Synthesis,Structure and Characterization of a New Complex: [Mn(C_6H_(12)N_4)_2(H_2O)_4][Mn(H_2O)_6][SO_4]_2·6H_2O

A novel complex,[Mn(C_6H_(12)N_4)_2(H_2O)_4][Mn(H_2O)_6][SO_4]_2·6H_2O,was synthesized and hexagonal single crystals with centimeter-scale sizes were obtained by the method of solvent evaporation.It was characterized by elemental analysis,infrared spectrum,thermogravimetric analysis and X-ray single-crystal diffraction.The complex belongs to triclinic crystal system,space group P■ with a=9.3390(8),b=13.3520(13),c=16.3207(13)?,α=100.7160(3)°,β=90.1020(10)°,γ=109.9490(5)°,V=1874.9(3)?~3,Z=2,D_c=1.542 g/cm~3,M_r=870.64,μ=0.876 mm~(-1),T=293(2) K,F(000)=916 and S=0.990.The crystal structure determination displayed a distorted octahedral geometry around the manganese atom,which is bound to two nitrogen atoms from hexamethylenetetramine,acting as monodentate ligands,and to four aqua ligands.Variable-temperature magnetic measurements of the complex indicate the presence of weak antiferromagnetic interaction between manganese centers.     

RESEARCH ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——CRYSTAL AND MOLECULAR STRUCTURE OF (C_5H_7S_2)_3[Mo_3(μ_3-S)(μ_2-S_2)_3Cl_7]

The space group of the title crystal is Pnam. The unit cell parameters are: a=17.226(4), b=14.306(7), c=15.074(4); z=4, Dobs=2.03g·cm~(-3), D_(calc)=2.063g·cm~(-3). The crystal structure was solved by the heavy atom method and refined by the full-matrix least-squares until the final conventional discrepancy factor was reduced to 0.068. The results of the investigation show that the crystal consists of trinuclear Mo cluster anions [Mo_3(μ_3-S)(μ_2-S_2)_3Cl_7]~(3-) together with planar (C_5H_7S_2)~ monocations, surrounding the cluster anions. In the cluster anion three Mo atoms, forming a nearly equilateral triangle (2.755(1), 2.755(1), 2.743(1)), are bound by a μ_3-S bridging atom, while each pair of Mo atoms is bridged further by a μ_2-S_2 ligand. Besides, each Mo atom is coordinated to two terminal Cl atoms, so that the coordination sphere of each Mo atom approaches closely a pentagonal bipyramid. In addition, a single Gl atom, not at all involved in the coordination spheres of the three Mo atom     

配合物[Tb(p-ClBA)_3(phen)]_2的结构和性能(英文)

Terbium p-chlorobenzoate complex with 1,10-phenanthroline, [Tb( p-ClBA)_3phen]_2 (1) has been obtained in the ethanol solution, where p-ClBA=p-chlorobenzoate and phen=1,10-phenanthroline. It crystallizes in the triclinic system, space group P1, a=1.008 1(2) nm, b=1.185 7(2) nm, c=1.431 1(3) nm, α=110.826(4)°, β=96.436(4)°, γ=101.737(4)°, Z=2. The two Tb(Ⅲ) ions are linked by four carboxylate groups through their bidentate bridging modes, forming a dimeric unit with crystallographic inversion center. Each terbium ion has an eight-coordinate geometry with four of the coordination sites occupied by four oxygen atoms from the four bridging carboxylates, respectively, two oxygen atoms from bidentate carboxylate, and the remaining positions occupied by two nitrogen atoms from a 1,10-phenanthroline molecule. The Tb(Ⅲ) ion adopt a distorted square antiprism coordination geometry. The excitation and luminescence data observed at room temperature show that the title complex emits very intensive green fluorescence under ultraviolet light. The result of thermal analysis indicates the complex [Tb(p-ClBA)_3phen]_2 is quite stable to heat. CCDC: 221921.     

间氯苯甲酸构筑的双核铽(Ⅲ)配合物的水热合成、晶体结构及荧光性质(英文)

<正>The complex[Tb_2(ClC_6H_4COO)_6(2,2'-bipy)_2]·(ClC_6H_4COOH)·(H_2O)with m-chlorobenzoic acid and 2,2'-bipy -ridine as ligands has been synthesized by means of hydrothermal way.Crystal data for this complex are as follows: monoclinic,space group P1,a=1.143 9(4) nm,6=1.211 6(4) nm,c=1.419 9(5) nm,α= 103.600(6)°,β=95.382(3)°,γ= 99.506(4)°,V=1.8684(10)nm~3,D_c=1.692 g·cm~(-3),Z=2,μ(Mo Kα)=2.236 mm~(-1),F(000)=943,final discrepancy factors R_1=0.052 0,wR_2=0.118 6.In the crystal,two neighboring Tb(Ⅲ) ions are bridged by four m-chlorobenzoic acid anions,and their end positions coordinate with one 2,2'-bipyridine molecule and one m-chlorobenzoic acid anions, respectively,giving a binuclear cage structure,of which the spacing between Tb(Ⅲ)…Tb(Ⅲ) is 0.408 1 nm.Each Tb(Ⅲ) ion coordinates with two nitrogen atoms and six oxygen atoms,giving an eight-coordinated distorted square antiprism geometry.The luminescent property of the complex is also studied.     

RESEARCH ON TRINUCLEAR MOLYBDENUM CLUSTER COMPOUNDS——CRYSTAL AND MOLECULAR STRUCTURES OF (Et_4N)_2[Mo_3(μ_3-O)(μ_2-Cl)_3(Oac)_2Cl_5]

The title compound forms black crystals shaped like pseudo-octahedrons, which belong to the orthorhombic system The space group is Pna 2_1 with unit cell parametrs of a=17.815(1), b=16.629(2), c=12.003(1), and with Z=4, D_(obs)=1.80g·cm~(-3), and D_(calc)=1.804g·cm~(-3). The crystal structure was solved by the heavy atom method and refiened by fullmatrix least-squares to a final conventional R factor of 0.048 for 2584 unique reflections with I≥σ(Ⅰ). The investigation confirms that the crystal structure consists of tetraethylammonium cations and trinuclear Mo cluster anions. The anion is a μ_3-O monocapped trinuclear cluster with an average Mo-Mo bond length of 2.60 (2). On the side of the Mo_3 triangular plane opposite to the μ_3-O atom, each two Mo atoms are bridged by a Cl atom with the result that these seven atoms (3 Me, 1 O and 3 Cl atoms)form an apex-deficient quasicubane configuration. In addition, each Mo atom is coordinated to three additional atoms resulting in a pseudo-octahedral geome     

Hydrothermal synthesis and fluorescence of YF3: Eu3+

<正>Europium(Ⅲ)-doped YF_3 is prepared by a hydrothermal process at 200℃.X-ray diffraction(XRD) pattern identifies the formation of YF_3 phase without detectable impurity.Environment scanning electron microscopy(ESEM) image shows the even size distribution of the samples with cubic morphology.The excitation and emission spectra of the rare earth ions doped YF_3 are investigated by fluorescence spectrophotometer.The excitation spectrum for 591 nm emission has several excitation bands at 320, 365,386,397 and 467 nm,and the main peak value was 397 nm.Typical Eu~(3+) emission peaks at 591 nm(~5D_0→~7F_1) and 612 nm (~5D_0→~7F_2) are observed when excited by 397 nm,and the strongest emission is 591 nm,demonstrating that the rare earth ions occupy the centrosymmetrical sites in YF_3.     

CRYSTAL AND MOLECULAR STRUCTURE OF {Fe_6Mo_2S_8(S-t-Bu)_6(OMe)_3}(Et_4N)_3

<正> Introduction. The title compound has been synthesized by reaction of {(SR)_2FeMoS_4}2-with {Fe_4(SR) 10}~2- (R=t-Bu) in methanol. It is interesting to note that the complex, which involves two {Fe_3MoS_4}cubane-like clusters, is generally regarded as the best model compound for molybdenum center of nitrogenase. The synthesis and property of {Fe_6Mo_2S_8(S-tBu)_6(OMe)_3}~3- have been discribed. Although it has previously been noted that the structure of this complex is similar to its tungsten analog, the detail structural report of the title compound has not yet been given.     

TIME RESOLVED SPECTRA OF Eu(MBA)_3 PHEN COMPLEXES

Time-resolved fluorescence spectra of europium methylbenzoates(MBA)with 1,10-phenanthroline(phen)have been measured at room temperature.Foreach of the europium chelates,where the ligand triple states lie above the ~5D_1 level ofEu~(3-),the spectra providc evidence that the Eu~(3-) ~5D_0 state is populated by nonradiativeenergy transfer from the higher-lying ~5D_1,state.The relaxation time for energy decayfrom ~5D_1 state is measured in the microcrystals to bc of the order of a fewmicroseconds.It is suggested that the ligand C=0 and C=C stretching vibrations andEu-O vibrations,chclate ring and benzene ring vibrations make importantcontributions to the relaxation process.The ~5D\-1—~5D\-0 relaxation time of Eu-(p-MBA)_3phen is shorter than those of Eu(m-MBA)_3phen and Eu(o-MBA)_3phensince nonradiative degradation to ~5D_0 from ~5D_1 appears to be more strongly influencedby the E_u~(3+)sites in the former.     

SYNTHESIS, CHARACTERIZATION AND STRUCTURE OF [Co(DBP)_2·3Py]_2·2CHCl_3

The mixed ligand complex of cobalt with dibutylphosphate (HDBP) and pyridine has been synthesized. Elemental analysis yields the result that the formula of this compound is Co(DBP)_2·3Py·CHCl_3 (Py=pyridine). The thermal analsyis, visible spectra and magnetic properties of it have been studied as well. Single crystal structural analysis shows that the crystal is triclinic with space group P and the unit cell parameters are as follows:a=14.490(10), α=90.37(4)°,b=15.721(7), β=96.04(5)°,c=20.109(12), γ=105.63(4)°.The final R factor is 0.0773. Two Co atoms are connected by two bridging DBP groups to form a dinuclear molecule [Co(DBP)_2·3Py]_2 which has a C_s, symmetry. Each cell contains two dinuclear molecules and four chloroform molecules. The cobalt is coordinated in an octahedral arrangement by three oxygen atoms and three nitrogen atoms, of which one oxygen atom comes from a monodentate DBP group, two oxygen atoms from two bridging DBP groups, and the three nitrogen atoms from the three pyridi     

Synthesis,Electrochemical and Fluorescent Properties of a New Zinc(Ⅱ) Complex through Self-assembly Reaction of 2,2'-Bipyridine-3,3'-dicarboxylic Acid

A new Zn(Ⅱ) complex [Zn(Phen)_2(C_(12)H_6O_4N_2)(H_2O)]·3H_2O with 2,2?-bipyridine-3,3?-dicarboxylic acid and 1,10-phenanthroline(Phen) as ligands was synthesized, and the crystal data are as follows: monoclinic, space group P2_(1/n), a=12.5581(11), b=17.3382(17), c=15.6687(14) ?, β=110.579(2)o, M_r=731.02, V=3193.9(5) ?~3, Dc=1.520 g/cm~3, Z=4, μ(Mo Kα)=0.833 mm~(-1), F(000)=1508, the final R=0.0431 and w R=0.0936. In the title complex, the central Zn(Ⅱ) ion is located in a distorted octahedral coordination environment. The electrochemical and fluorescent properties were studied. The title complex possesses irreversible electron transfer in the electrode reaction, and it has a strong emission peak in the range of 470~505 nm, with the excitation wavelength being 488 nm.     

STUDY ON STRUCTURE OF SULFUR-BRIDGED TRANSITION METAL CLUSTERS——CRYSTAL AND MOLECULAR STRUCTURE OF (C_5H_7S_2)_3 [Mo_3(μ_3-S)_2 (μ_2-Cl)_3Cl_6]

The compound (C_5H_7S_2)_3[Mo_3 (μ_3--S)_2 (μ_2--Cl)_3 Cl_6] forms dark black octahedralcrystals with the following crystallographic parameters: a=22.885(10)A, c=25.407(7)A. Thespace group is I4_1/α, Z=16, ρ_(obs.)=2.073g/cm~3, ρ_(calc.)=2.126g/cm~3. The 1621 independentreflections with I≥3σ were collected on a CAD-4 four-circle diffractometer by means of MoK_αradiation. The structure was solved by three-dimensional Patterson synthesis and refined byleast squares technique to a final discrepancy factor of R=0.056. The results of our investiga-tion reveal that the molecule consists of a trinuclear Mo cluster anion and three planar mono-cations.surrounding the cluster anion. As the core of the anion the triad of Mo atoms, possessing anequilateral triangular configuration, is linked by two μ3--S bridging atoms and three μ2--Clatoms. Besides, two terminal Cl atoms are attached to each Mo atom to form an octahedralconfiguration. The diamagnetism and the short Mo-Mo distances (2.556 A, 2.641 A, 2.653 A)clearly indicate the existence of Mo-Mo bonds. The anion as a whole has an idealized D_(3h) localsymmetry.     

高藜芦酸邻菲咯啉铽(Ⅲ)配合物的合成、晶体结构及荧光光谱

A terbium(Ⅲ) complex [Tb2(NO3)(DMPA)5(phen) 2] (HDMPA=homoveratric acid, C12H12O4; phen=1,10- phenanthroline), was synthesized and characterized by elemental analysis, IR and TG-DTG. Its crystal structure was determined by single crystal X-ray diffraction method. The complex, C74H71N5O23Tb2, crystallizes in the monoclinic system, space group P21/n. The emission spectrum of complex, there are four main peaks, 489, 545, 584 and 622 nm, respectively, corresponding to 5D4→7F6, 5D4→7F5, 5D4→7F4 and 5D4→7F3 transitions of Tb(Ⅲ). The intensity of 5D4→7F5 is much stronger than others.