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1.
利用2,6-二氟苯甲酸和1,10-菲咯啉作为配体分别与Tm~(3+)、Yb~(3+)离子在常温下反应,制得2个稀土配合物[Tm(dfba)_2(phen)(μ_2-dfba)]_2 (1)和[Yb(dfba)_2(phen)(μ_2-dfba)]_2 (2)(dfba~-=2,6-二氟苯甲酸根,phen=1,10-菲咯啉)。用元素分析、红外光谱对2个稀土配合物进行了表征,并用单晶X射线衍射确定了配合物的晶体结构;测定了配合物1和2的热稳定性。结构分析表明配合物1和2具有相似的晶体结构。每个Ln~(3+)与2个dfba~-配体和1个phen分子配位,形成[Ln(dfba)_2(phen)]~+结构单元,[Ln(dfba)_2(phen)]~+单元再通过2个不同的dfba~-配体桥联形成双核分子[Ln(dfba)_2(phen)(μ_2-dfba)]_2(Ln=Tm,Yb)。  相似文献   

2.
孙长艳  李杨  李文军  车平 《无机化学学报》2013,29(10):2140-2144
由水热法合成了2个微孔镧系超分子配合物[Ln(CCA)(OH)(phen)(H2O)]n·n(phen)·nH2O(Ln=Yb,1;Er,2;H2CCA=2-羧基肉桂酸;phen=1,10-菲啰啉),并用元素分析、IR及X-射线单晶衍射对其进行了表征。晶体结构研究表明,2个配合物都是由配体2-羧基肉桂酸连接而形成的一维双链结构,该链状结构通过氢键和π-π堆积作用扩展为具有微孔结构的超分子。1,10-菲啰啉在微孔结构的形成过程中起到了模板剂的作用。  相似文献   

3.
用水热法和溶液法分别合成了2个新的配合物{[Ag(4,4′-bpy)]·3-HSBA.H2O}n(1)和[Zn(phen)2(H2O)2]·(A-2,5-DSA)·3H2O(2)(3-HSBA=3-羧基苯磺酸根,A-2,5-DSA=苯氨-2,5-二磺酸根,4,4′-bpy=4,4′-联吡啶,phen=1,10-邻菲咯啉),用X-射线单晶衍射结构分析方法测定了其晶体结构。配合物1是一维链状结构。在1个不对称单元中包含1个[Ag(4,4′-bpy)]+阳离子,1个3-羧基苯磺酸根阴离子和1个晶格水分子。Ag髣离子与2个4,4′-联吡啶的2个氮原子配位。配合物2是单核结构。在1个不对称单元中包含1个[Zn(phen)2(H2O)2]2+阳离子,1个苯氨-2,5-二磺酸根阴离子和3个晶格水分子。Zn髤离子与2个1,10-邻菲咯啉的4个氮原子和2个水氧原子配位。配合物1和2中,配位阳离子、抗衡阴离子以及晶格水分子之间存在丰富的氢键,进而构筑成超分子网络结构。配合物的荧光均来自于配体的π-π*电子跃迁。  相似文献   

4.
用水热法和溶液法分别合成了2个新的配合物{[Ag(4,4′-bpy)]·3-HSBA.H2O}n(1)和[Zn(phen)2(H2O)2]·(A-2,5-DSA)·3H2O(2)(3-HSBA=3-羧基苯磺酸根,A-2,5-DSA=苯氨-2,5-二磺酸根,4,4′-bpy=4,4′-联吡啶,phen=1,10-邻菲咯啉),用X-射线单晶衍射结构分析方法测定了其晶体结构。配合物1是一维链状结构。在1个不对称单元中包含1个[Ag(4,4′-bpy)]+阳离子,1个3-羧基苯磺酸根阴离子和1个晶格水分子。Ag髣离子与2个4,4′-联吡啶的2个氮原子配位。配合物2是单核结构。在1个不对称单元中包含1个[Zn(phen)2(H2O)2]2+阳离子,1个苯氨-2,5-二磺酸根阴离子和3个晶格水分子。Zn髤离子与2个1,10-邻菲咯啉的4个氮原子和2个水氧原子配位。配合物1和2中,配位阳离子、抗衡阴离子以及晶格水分子之间存在丰富的氢键,进而构筑成超分子网络结构。配合物的荧光均来自于配体的π-π*电子跃迁。  相似文献   

5.
合成了三种稀土元素与牛磺酸缩邻香草醛Schiff碱的配合物[Ln(TOv)(phen)(NO3)]·2H2O(TOv:牛磺酸缩邻香草醛Schiff碱配体;phen:1,10-邻菲哕啉;Ln:Er,Tm,Yb),并对其进行了结构表征.采用Achar微分法和Coats.Redfem积分法拟合得到了配合物的热分解动力学方程.  相似文献   

6.
合成了三种稀土元素与牛磺酸缩邻香草醛Schiff碱的配合物[Ln(TOv)(phen)(NO3)]·2H2O(TOv:牛磺酸缩邻香草醛Schiff碱配体;phen:1,10-邻菲哕啉;Ln:Er,Tm,Yb),并对其进行了结构表征.采用Achar微分法和Coats.Redfem积分法拟合得到了配合物的热分解动力学方程.  相似文献   

7.
利用混合配体(H2tda=亚硫基二乙酸,H2ox=乙二酸,phen=1,10-菲咯啉)与CeCl3.5H2O反应,合成了新型稀土配合物[Ce(tda)(ox)0.5(phen)]n,单晶结构分析表明:配合物以共边的多面体[Ce2O12N4]为基本单元构筑二维结构,并通过π-π堆积作用拓展为三维超分子体系。该二维结构具有(4,5)连接的(46)(4.466)2拓扑结构,在拓扑结构中稀土离子呈现不寻常的5连接点。  相似文献   

8.
合成了2个新的配合物[Zn(BPP)2(H2O)4](2,6-NDS)·0.5H2O(1)和[Ni(phen)2(H2O)2](A-2,5-DSA)·3H2O(2)(2,6-NDS=2,6-萘二磺酸根,A-2,5-DSA=苯氨-2,5-二磺酸根,BPP=1,3-二(4-吡啶基)丙烷,phen=1,10-邻菲咯啉),用X-射线单晶衍射结构分析方法测定了配合物的晶体结构。配合物1是单核分子,Zn2+离子与2个1,3-二(4-吡啶基)丙烷的2个N原子及4个水分子配位,形成单核配位阳离子。相邻配位阳离子通过配位水分子与氮原子的氢键作用联接成一维双螺旋阳离子链。双螺旋阳离子链与未配位的2,6-萘二磺酸根阴离子通过氢键作用形成二维超分子网。配合物2是单核分子,Ni2+离子与2个1,10-邻菲咯啉分子中的4个N原子及2个水分子配位,形成单核配位阳离子。配位阳离子与游离的水分子及苯氨-2,5-二磺酸根阴离子通过氢键作用构筑成二维超分子网。  相似文献   

9.
以5-羟基间苯二甲酸(HO-H2bdc)、5-甲基间苯二甲酸(m-H2bdc)和1,10-菲啰啉(phen)为配体,在水热条件下合成了饵金属-有机骨架[Er2(HO-bdc)2(m-bdc)(phen)].3H2O。通过X-射线单晶衍射仪测定其晶体结构,结果表明该化合物包含一个三维[Er2(HO-bdc)2(m-bdc)(phen)]框架,而结晶水分子位于其中。该化合物中丰富的氢键作用和1,10-菲啰啉芳香环之间的π-π堆积作用进一步稳固了其三维结构。  相似文献   

10.
通过水热法合成了2个新的金属-有机超分子配合物[Ni(eoba)(phen)(H_2O)_2]·0.58H_2O(1)和[Co(eoba)(phen)]2·H_2O(2)(H_2boba=4,4′-(乙烷-1,2-二氧基)-二苯甲酸,phen=菲咯啉),并对其进行了元素分析、红外光谱、热重和X射线单晶衍射测定。配合物1和2是同构的,每个配合物都是六配位的,菲咯啉分子上的2个氮原子、4,4′-(乙烷-1,2-二氧基)-二苯甲酸配体上的2个氧原子和2个配位水分子与金属配位。此外,还用高斯09程序PBE0/LANL2DZ方法对配合物1进行了自然键轨道(NBO)分析,计算结果表明配位原子与Ni原子之间存在着共价作用。  相似文献   

11.
Russian Chemical Bulletin - Electronic structures of a series oflanthanide complexes with hexafluoroisopropoxide ligands [Ln(OCH(CF3)2)2(μ2-OCH(CF3)2)(DME)]2 (Ln = Ce, Sm, Tm, Yb; DME is...  相似文献   

12.
Rare earth metals activated with ca. 2% iodine react directly with 2,6-diisopropylphenol (HOdip) in tetrahydrofuran (thf), 1,2-dimethoxyethane (dme), and dig-dme (dig = di(2-methoxyethyl) ether) to give solvated phenolate complexes [Ln(Odip)(3)(thf)(n)] (Ln = La, Nd, n = 3; Ln = Sm, Dy, Y, Yb, n = 2), [Eu(Odip)(μ-Odip)(thf)(2)](2), [Ln(Odip)(3)(dme)(2)] (Ln = La, Yb) and [La(Odip)(3)(dig)] in good yield for Ln = La, Nd, Eu but modest yield for smaller Ln metals under comparable conditions. However, increasing the excess of metal greatly increased the yield for Ln = Y. The synthetic method has general potential, at least for lanthanoid phenolates. Comparison redox transmetallation/protolysis (RTP) reactions between Ln metals, Hg(C(6)F(5))(2) and the phenol gave higher yields in shorter time and, for Eu, gave [Eu(Odip)(3)(thf)(3)] in contrast to an Eu(II) complex from Eu(I(2)). New [Ln(Odip)(3)(thf)(3)] complexes have fac-octahedral structures and [Ln(Odip)(3)(thf)(2)] monomeric five coordinate distorted trigonal bipyramidal structures with apical thf ligands. [Eu(Odip)(μ-Odip)(thf)(2)](2) is an unsymmetrical dimer with two bridging Odip ligands. One five coordinate Eu atom has distorted trigonal bipyramidal stereochemistry and the other is distorted square pyramidal. Whilst [La(Odip)(3)(dme)(2)] has irregular seven coordination with mer-Odip and chelating dme ligands, [Ln(Odip)(3)(dme)(2)] (Ln = Dy, Y (prepared by ligand exchange), Yb) are monomeric six coordinate with one chelating and one unidentate dme. A six coordinate fac-octahedral arrangement is observed in [La(Odip)(3)(dig)].  相似文献   

13.
Reactions of a range of the readily prepared and sterically tunable N,N'-bis(aryl)formamidines with lanthanoid metals and bis(pentafluorophenyl)mercury (Hg(C6F5)2) in THF have given an extensive series of tris(formamidinato)lanthanoid(III) complexes, [Ln(Form)3(thf)n], namely [La(o-TolForm)3(thf)2], [Er(o-TolForm)3(thf)], [La(XylForm)3(thf)], [Sm(XylForm)3], [Ln(MesForm)3] (Ln=La, Nd, Sm and Yb), [Ln(EtForm)3] (Ln=La, Nd, Sm, Ho and Yb), and [Ln(o-PhPhForm)3] (Ln=La, Nd, Sm and Er). [For an explanation of the N,N'-bis(aryl)formamidinate abbreviations used see Scheme 1.] Analogous attempts to prepare [Yb(o-TolForm)3] by this method invariably yielded [{Yb(o-TolForm)2(mu-OH)(thf)}2], but [Yb(o-TolForm)3] was isolated from a metathesis synthesis. X-ray crystal structures show exclusively N,N'-chelation of the Form ligands and a gradation in coordination number with Ln3+ size and with Form ligand bulk. The largest ligands, MesForm, EtForm and o-PhPhForm give solely homoleptic complexes, the first two being six-coordinate, the last having an eta1-pi-Ar--Ln interaction. Reaction of lanthanoid elements and Hg(C6F5)2 with the still bulkier DippFormH in THF resulted in C--F activation and formation of [Ln(DippForm)2F(thf)] (Ln=La, Ce, Nd, Sm and Tm) complexes, and o-HC6F4O(CH2)4DippForm in which the formamidine is functionalised by a ring-opened THF that has trapped tetrafluorobenzyne. Analogous reactions between Ln metals, Hg(o-HC6F4)2 and DippFormH yielded [Ln(DippForm)2F(thf)] (Ln=La, Sm and Nd) and 3,4,5-F3C6H2O(CH2)4DippForm. X-ray crystal structures of the heteroleptic fluorides show six-coordinate monomers with two chelating DippForm ligands and cisoid fluoride and THF ligands in a trigonal prismatic array. The organometallic species [Ln(DippForm)2(C[triple chemical bond]CPh)(thf)] (Ln=Nd or Sm) are obtained from reaction of Nd metal, bis(phenylethynyl)mercury (Hg(C[triple chemical bond]CPh)2) and DippFormH, and the oxidation of [Sm(DippForm)2(thf)2] with Hg(C[triple chemical bond]CPh)2, respectively. The monomeric, six-coordinate, cisoid [Ln(DippForm)2(C[triple chemical bond]CPh)(thf)] complexes have trigonal prismatic geometries and rare (for Ln) terminal C[triple chemical bond]CPh groups with contrasting Ln--C[triple chemical bond]C angles (Ln=Nd, 170.9(4) degrees; Ln=Sm, 142.9(7) degrees). Their formation lends support to the view that [Ln(DippForm)2F(thf)] complexes arise from oxidative formation and C--F activation of [Ln(DippForm)2(C6F5)] intermediates.  相似文献   

14.
Two series of novel complexes, [Ln(dca)(2)(Phen)(2)(H(2)O)(3)](dca).(phen) (Ln = Pr (1), Gd (2), and Sm (3), dca = N(CN)(-), phen = 1,10-phenanthroline) and [Ln(dca)(3)(2,2'-bipy)(2)(H(2)O)](n), (Ln = Gd (4), Sm (5), and La (6), 2,2'-bipy = 2,2'-bipydine), have been synthesized and structurally characterized by X-ray crystallography. The crystal structures of the first series (1-3) are isomorphous and consist of discrete [Ln(dca)(2)(Phen)(2)(H(2)O)(3)]+ cations, dca anions, and lattice phen molecules; whereas the structures of the second series (4-6) are characterized by infinite chains [Ln(dca)(3)(2,2'-bipy)(2)(H(2)O)](n). The Ln(III) atoms in all complexes are nine-coordinated and form a distorted tricapped trigonal prism environment. The three-dimensional frameworks of 1-6 are constructed by intermolecular hydrogen bond interactions. Variable-temperature magnetic susceptibility measurements for complexes 1, 2, 4, and 5 indicate a Curie-Weiss paramagnetic behavior over 5-300 K.  相似文献   

15.
We report the synthesis of Ln3+ nitrate [Ln(Tpm)(NO3)3] ⋅ MeCN (Ln=Yb ( 1Yb ), Eu ( 1Eu )) and chloride [Yb(Tpm)Cl3] ⋅ 2MeCN ( 2Yb ), [Eu(Tpm)Cl2(μ-Cl)]2 ( 2Eu ) complexes coordinated by neutral tripodal tris(3,5-dimethylpyrazolyl)methane (Tpm). The crystal structures of 1Ln and 2Ln were established by single crystal X-ray diffraction, while for 1Yb high resolution experiment was performed. Nitrate complexes 1Ln are isomorphous and both adopt mononuclear structure. Chloride 2Yb is monomeric, while Eu3+ analogue 2Eu adopts a binuclear structure due to two μ2-bridging chloride ligands. The typical lanthanide luminescence was observed for europium complexes ( 1Eu and 2Eu ) as well as for terbium and dysprosium analogues ([Ln(Tpm)(NO3)3] ⋅ MeCN, Ln=Tb ( 1Tb ), Dy ( 1Dy ); [Ln(Tpm)Cl3] ⋅ 2MeCN, Ln=Tb ( 2Tb ), Dy ( 2Dy )).  相似文献   

16.
The acid-base reaction of [Ln(CH(2)SiMe(3))(3)(thf)(2)] with Cp'H gave the corresponding half-sandwich rare earth dialkyl complexes [(Cp')Ln(CH(2)SiMe(3))(2)(thf)] (1-Ln: Ln=Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; Cp'=C(5)Me(4)SiMe(3)) in 62-90% isolated yields. X-ray crystallographic studies revealed that all of these complexes adopt a similar overall structure, in spite of large difference in metal-ion size. In most cases, the hydrogenolysis of the dialkyl complexes in toluene gave the tetranuclear octahydride complexes [{(Cp')Ln(μ-H)(2)}(4)(thf)(x)] (2-Ln: Ln=Sc, x=0; Y, x=1; Er, x=1; Tm, x=1; Gd, x=1; Dy, x=1; Ho, x=1) as the only isolable product. However, in the case of Lu, a trinuclear pentahydride [(Cp')(2)Lu(3)(μ-H)(5)(μ-CH(2)SiMe(2)C(5)Me(4))(thf)(2)] (3), in which the C-H activation of a methyl group of the Me(3)Si unit on a Cp' ligand took place, was obtained as a major product (66% yield), in addition to the tetranuclear octahydride [{(Cp')Lu(μ-H)(2)}(4)(thf)] (2-Lu, 34%). The use of hexane instead of toluene as a solvent for the hydrogenolysis of 1-Lu led to formation of 2-Lu as a major product (85%), while a similar reaction in THF yielded 3 predominantly (90%). The tetranuclear octahydride complexes of early (larger) lanthanide metals [{Cp'Ln(μ-H)(2)}(4)(thf)(2)] (2, Ln=La, Ce, Pr, Nd, Sm) were obtained in 38-57% isolated yields by hydrogenolysis of the bis(aminobenzyl) species [Cp'Ln(CH(2)C(6)H(4)NMe(2)-o)(2)], which were generated in-situ by reaction of [Ln(CH(2)C(6)H(4)NMe(2)-o)(3)] with one equivalent of Cp'H. X-ray crystallographic studies showed that the fine structures of these hydride clusters are dependent on the size of the metal ions.  相似文献   

17.
The ferrocene-derivatives bis(ferrocenyl-ethynyl)-1,10-phenanthroline (Fc(2)phen) and ferrocenoyltrifluoroacetone (Hfta) have been used to synthesize ferrocene-containing rare-earth beta-diketonate complexes. The complexes [Ln(tta)(3)(Fc(2)phen)] and [Ln(fta)(3)(phen)] (where Ln = La, Nd, Eu, Yb) show structural similarities to the tris(2-thenoyltrifluoroacetonate)(1,10-phenanthroline)lanthanide(III) complexes, [Ln(tta)(3)(phen)]. The coordination number of the lanthanide ion is 8, and the coordination sphere can be described as a distorted dodecahedron. However, the presence of the ferrocene moieties shifts the ligand absorption bands of the rare-earth complexes to longer wavelengths so that the complexes can be excited not only by ultraviolet radiation but also by visible light of wavelengths up to 420 nm. Red photoluminescence is observed for the europium(III) complexes and near-infrared photoluminescence for the neodymium(III) and ytterbium(III) complexes. The presence of the ferrocene groups makes the rare-earth complexes hydrophobic and well-soluble in apolar organic solvents.  相似文献   

18.
This paper describes syntheses and structure determination of four lanthanide complexes [Nd(2-Cl-4-FBA) 3 phen] 2 (1, 2-Cl-4-FBA = 2-chloro-4-fluorobenzoate, phen = 1,10-phenanthroline), [Ln(2,5-DClBA) 3 phen] 2 (Ln = Sm(2) and Tb(3), 2,5-DClBA = 2,5-dichlorobenzoate) and [Sm(2-Cl-4,5-DFBA) 3 (phen)(H 2 O)] 2 (4, (2-Cl-4,5-DFBA = 2-chloro-4,5-difluorobenzo- ate). The complexes were characterized by elemental analysis, infrared and ultraviolet spectra, and X-ray single-crystal diffraction. In the molecular structures of 1 4, two Ln 3+ ions are linked by four carboxyl groups, with two of them in a bridging bidentate mode and the other two in a bridging-chelating tridentate mode, forming four binuclear molecules. In addition, each Ln 3+ ion is also chelated to one phen molecule and one carboxyl group in the complexes, except each Sm 3+ ion in 4 which is bonded to one carboxyl group by unidentate mode and one H 2 O molecule. There are two different coordination polyhedrons for each Nd 3+ ion in the two similar molecular structures of 1 and they are a distorted monocapped square antiprismatic and a distorted tricapped triangular prism conformation, respectively. The coordination polyhedron for each Ln 3+ ion in 2 4 is a nine-coordinated distorted mono-capped square antiprismatic conformation. The complex 3 exhibits green luminescence under the radiation of UV light. The thermal decomposition behaviors of the complexes have been discussed by simultaneous TG/DSC-FTIR technique. The 3D surface graphs for the FTIR spectra of the evolved gases were recorded and the gaseous products were identified by the typical IR spectra obtained at different temperatures from the 3D surface graphs. Meanwhile, we discussed the nonisothermal kinetics of 1 4 by the integral isoconversional non-linear (NL-INT) method.  相似文献   

19.
First heterometal-organic single source precursors for NaYF(4) nanomaterials as a host matrix for up-conversion emission are reported. These novel heterobimetallic derivatives NaY(TFA)(4)(diglyme) (1), [Na(triglyme)(2)][Y(2)(TFA)(7)(THF)(2)] (2) and Na(2)Y(TFA)(5)(tetraglyme) (3) (TFA = trifluoroacetate), which were fully characterized by elemental analysis, FT-IR and (1)H NMR spectroscopy, TG-DTA data as well as single crystal X-ray structures, are advantageous in terms of being anhydrous and having lower decomposition temperatures in comparison to the homometallic precursor Y(TFA)(3)(H(2)O)(3). In addition, they also contain chelating glyme ligands, which act as capping reagents during decomposition to control the NaYF(4) particle size and render them monodisperse in organic solvents. On decomposition in 1-octadecene, the molecular derivatives 1 and 3 are converted, in the absence of any surfactant or capping reagent, to cubic NaYF(4) nanocrystals at significantly lower temperatures (below 250 °C). At higher temperature, a mixture of the cubic and hexagonal phases was obtained, the relative ratio of the two phases depending on the reaction temperature. A pure hexagonal phase, which is many folds more efficient for UC emission than the cubic phase, was obtained by calcining nanocrystals of mixed phase at 400 °C. In order to co-dope this host matrix with up-converting lanthanide cations, analogous complexes NaLn(TFA)(4)(diglyme) [Ln = Er (4), Tm (5), Yb (6)] and Na(2)Ln(TFA)(5)(tetraglyme) [Ln = Er (7), Yb (8)] were also prepared and characterized. The decomposition in 1-octadecene of suitable combinations and appropriate molar ratios of these yttrium, ytterbium and erbium/thulium derivatives gave cubic and/or hexagonal NaYF(4): Yb(3+), Er(3+)/Tm(3+) nanocrystals (NCs) capped by diglyme or tetraglyme ligands, which were characterized by IR, TG-DTA data, EDX analysis and TEM studies. Surface modification of these NCs by ligand exchange reactions with poly acrylic acid (PAA) and polyethyleneglycol (PEG) diacid 600 was also carried out to render them water soluble. The THF solutions of suitable combinations of the diglyme derivatives were also used to elaborate the thin films of NaYF(4):Yb(3+), Er(3+)/Tm(3+) on a glass or Si wafer substrate by spin coating. The multicolour up-conversion fluorescence was successfully realized in the Yb(3+)/Er(3+) (green/red) and Yb(3+)/Tm(3+) (blue/violet) co-doped NaYF(4) nanoparticles and thin films, which demonstrates that they are promising UC nanophosphors of immense practical interest. The up-conversion excitation pathways for the Er(3+)/Yb(3+) and Tm(3+)/Yb(3+) co-doped materials are discussed.  相似文献   

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