Synthesis and Crystal Structure of a Novel Organolanthanide Schiff Base Complex[(η~5-C_5H_5)Pr(acac)_2(μ_3-OH)]_2·4THF

The title complex (h5-C5H5)Pr(acac)2(m3-OH)]24THF was prepared by the reaction of Cp3Pr with equimolar bis(acetylacetone)ethylenediamine (H2acac) in THF, and its crystal structure was characterized by X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a =13.286(2), b =13.121(2), c = 23.95(1) ? = 93.50(2)? V = 4167(1) ?, Z = 2, C74H116O14N8Pr4, Mr = 1905.41, Dc = 1.523 g/cm3, F(000) = 1940 and ?MoK? = 23.51 cm-1 (?= 0.7107 ?. The final R and Rw are 0.033 and 0.046, respectively with 5968 observed reflections. It is a partially hydrolytic product, containing hydroxyl bridge in a m3-fashion. The molecular structure shows that there exist two symmetrical units collected via two hydroxide groups and two oxygen atoms from the Schiff base ligands. In each unit, there are two praseodymium atoms with different coordination.

Synthesis and Crystal Structure of [(Praseodymium)_2(3,5-Binitro Benzoyloxy)_6 (Dimethyl Sulfoxide)_4] Complex

A novel one-dimensional chain complex [Pr2(bnbo)6(DMSO)4] (bnbo=3,5-binitro benzoyloxy, DMSO= dimethyl sulfoxide) with bridging carboxyl groups was synthesized and its structure has been determined by single-crystal X-ray methods. In the complex, a pair of adjacent metal ions are alternately connected by four or two carboxylate groups to form an infinite chain of 8-coordinated Pr3+ ions. The complex (Pr2C50H42N12O40S4 ) crystal system is triclinic, with space group P1, a=14.2890(3), b=14.3427(3), c=20.1601(2)? =76.636(1), b=84.496(1), =60.316(1)? V=3491.4(1)?, Z=2, Mr =1861.02, Dc=1.770 g/cm3, m=1.608mm-1, F(000)=1856, the final R=0.0776 and wR=0.1724 for 8804 reflections with I > 2s(I).

Synthesis and Crystal Structure of a New Praseodymium(Ⅲ)-Copper(Ⅱ)Polymeric Complex:〔Pr_(2)Cu_(3)(L_(1))_(6)〕_(n)(H_(2)L_(1)=NH{CH_(2)COOH}_(2))

A novel polymeric Pr 2Cu 3 complex of iminodiacetic acid (H 2L 1=NH{CH 2COOH} 2) Pr 2Cu 3(L 1) 6 n , 1, has been synthesized and structurally characterized. The title complex Pr 2Cu 3O 24 N 6C 24 H 30 ( M r =1258.97) crystallized in trigonal space group P3 c1 (No. 165) with a = 13.424(4), c=14.752(6); V=2303(1) 3; F(000)=1226; λ (Mo Kα )=35.2 cm -1 ; D c =1.820 g·cm -3 ; Z =2. The final R and R w are 0.072 and 0.081 respectively for 1412 reflections with I】3σ(I) . In crystal 1, the Pr 3+ ion is nine coordinated by 6 O atoms from three bidentate chelating carboxylate groups and 3 O atoms from three anti anti bridging carboxylic groups of six L 1 ligands; the Cu 2+ ion is six coordinated by 4 O and 2 N atoms from two pentadentate L 1 ligands. Each pair of Pr(Ⅲ) atoms is bridged by three L 1 ligands, each of which also chelates with one copper(Ⅱ) ion, thus forming a Pr 2Cu 3 cluster unit. Such cluster units are cross linked by flexible L 1 ligands into a three dimensional coordination framework.

Synthesis, Structure and Luminescent Properties of a Nine-Coordinated Praseodymium Complex

The Pr(TTA)_3phen(C_2H_5OH)quarternary complex with 2-thenoyltrifluoro-acetone(TTA), 1,10-phenanthroline(phen)and ethanol were synthesized and characterized by single-crystal X-ray diffraction. The central Pr^(3+) ion is nine-coordinated. The infrared(IR)spectrum, diffuse reflectance(DR)spectrum and fluorescence measurements of the complex were investigated.

Synthesis and Crystal Structure of a Novel 1D Coordination Polymer:[Pr(BYBA)_3(H_2O)_2]·[Pr(BYBA)_3(H_2O)]

The novel coordination polymer [Pr（BYBA）3（H2O）2]·[Pr（BYBA）3（H2O）] （BYBAH = 2-benzoylbenzoic acid） was yielded by hydrothermal synthesis, determined by single-crystal X-ray diffraction, and characterized by FT-IR and UV-Vis spectra. The crystal crystallizes in the triclinic system, space group P1 with a = 9.112（3）, b = 14.644（5）, c = 27.076（11） A, α = 84.223（3）,β = 87.816（4）,γ = 88.902（4）°, V= 3592（2）A, C84H60O21Pr2, Mr = 1687.14, Z = 2, F（000） = 1700, Dc = 1.560 g/cm^3, μ=1.419mm^-1, the fmal R = 0.0485 and wR = 0.1258 for 13035 observed reflections with I 〉 2σ（Ⅰ）. The compound contains two different building milts, [Pr2（BYBA）6（H2O）4] and [Pr2（BYBA）6（H2O）2]. It is noticeable that [Pr2（BYBA）6（H2O）4] is an isolated binuclear building block, in which the Pr3＋ ion centers are both located in an eight-coordinated environment. However, in [Pr2（BYBA）6（H2O）2] the Pr^3＋ ion centers are located in a nine-coordinated envirormlent and connected by BYBA ligands to form 1D chains.

Studies on Organolanthanide Complexes(L)——Syntheses and Crystal Structures of(CH_3OCH_2CH_2C_5H_4)_2 SmI and(CH_3OCH_2CH_2C_5H_4)SmI_2·2THF

Reactions of samarium triiodides with 2 equivalents of potassium 2-methoxyethyl- cyelopentadienyl or 1 equivalent of potassium 2-methoxyethylcyclopentadienyl in tetrehydrofuran afford bis- (2-methoxyethylcyclopentadienyl) samarium iodide complex Cp′_2 SmI 1 (Cp′=MeOCH_2CH_2C_5H_4),and (2- methoxyethylcyclopentadienyl) samarium diioidide complex Cp′SmI_2·2THF 2.Compound 1 crystallizes from THF/hexane in orthorhombic space group P2_12_12_1 with cell dimensions a= 11.074(4),b= 12.929(9), c=12.269(4) ,V=1756.9 ~3 and D_(cacld)=1.978 g/cm^3 for Z=4.The central metal Sm is coordinated with two Cp′ ring centroids,one iodine atom and two oxygen atoms of Cp′ forming a distorted trigonal bipyramid.The coordination number of Sm (Ⅲ) in 1 is 9.The crysal of 2 belongs to the monoclinie crystal system,space group P2_1/c with a=16.304(6),b=8.335(2),c=16.527(5) ,β=111.8 (1)°,V= 2085.3 ~3 D_(cacld)=2.138 g/cm^3 and Z=4.The central metal Sm is coordinated by one Cp′ ring centroid, two iodine atoms,one oxygen atom of Cp′ and two oxygen atoms of THF forming a distorted octahedron. The coordination number of Sm (Ⅲ) in 2 is 8.

Crystal Structure of Praseodymium Complex with L－proline，Pr_2（L－Pro）_6（H_2O）_4·6ClO_4

Pr2(L-Pro)6(H2O)4]·6ClO4(Pro= proline), Mr=1641.4, monoclinic, P21,α=9. 879(3),b=21. 883(4),c=13. 393(2) A, β=91. 23(2) A, V=2895(1) A3, Z=2,Dc=1. 88g/cm3,μ( MoKα)=20. 5cm￣(-1) . F(000)=1648, R =0. 035 for 5032 observed reflections. The coordination polyhedron of Pr( Ⅲ) ion comprises six oxygen atoms from the L-Pro molecules and two from the water molecules, Each L-Pro molecule coordinates to two Pr(Ⅲ) ions through the carboxyl oxygens in a bidentate bridging mode, thus creating one-dimensional chain structure.

Crystal Structure of Praseodymium Complex with L－proline，Pr2（L－Pro）6（H2O）4·6ClO4

Pr2(L-Pro)6(H2O)4]·6ClO4(Pro= proline), Mr=1641.4, monoclinic, P21,α=9. 879(3),b=21. 883(4),c=13. 393(2) A, β=91. 23(2) A, V=2895(1) A3, Z=2,Dc=1. 88g/cm3,μ( MoKα)=20. 5cm￣(-1) . F(000)=1648, R =0. 035 for 5032 observed reflections. The coordination polyhedron of Pr( Ⅲ) ion comprises six oxygen atoms from the L-Pro molecules and two from the water molecules, Each L-Pro molecule coordinates to two Pr(Ⅲ) ions through the carboxyl oxygens in a bidentate bridging mode, thus creating one-dimensional chain structure.

Synthesis and Crystal Structure of the Binuclear Complex [Pr2（C10H8N2O4）2（C10H9N2O4）2（H2O）4]·3H2O·C6H6

The binuclear praseodymium（Ⅲ） complex with N-（1-carboxyethylidene）-salicylhydrazide （C10H10N2O4, H2L） was prepared in H2O-C2H5OH mixed solution, and the crystal structure of [Pr2L2（HL）2（H2O）4]·3H2O·C6H6 was determined by X-ray single crystal diffraction. The crystal complex crystallizes in the triclinic system with space group P-1, and in the structure each Pr atom is 9-coordinated by carboxyl O and acyl O and azomethine N atoms of two tridentate ligands to form two stable five-membered rings sharing one side in keto-mode and two water molecules. The coordination polyhedron around Pr^3＋ was described as a monocapped square antiprism geometry. In an individual molecule, four tridentate ligands were coordinated by two negative univalent （HL） and two bivalent forms （L） respectively. Two negative univalent ligands were coordinated via μ2-bridging mode.

Two Praseodymium Coordination Complexes with 1,3-Phenylenediacetate:Structural Diversity Tuned by Auxiliary Ligands

Two new coordination complexes, [Pr（1,3-pda）0.5（nbca）2（H2O）2]（1） and [Pr2（1,3-pda）3（2,2ˊ-bpy）2（H2O）2]（2）（H2pda = 1,3-phenylenediacetic acid, Hnbca = 5-nitro [1,1ˊ-biphenyl]-3-carboxylic acid, 2,2ˊ-bpy = 2,2ˊ-bipyridine）, have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. In 1, the nbca ligands bridge the Pr3＋ ions to form a 1D chain. Moreover, these 1D chains are united together through the 1,3-pda ligands to afford a 2D layer. In contrast, due to a different auxiliary ligand, complex 2 is a 2D layer linked through only bridging deprotonated 1,3-pda. Thermal stabilities and solid fluorescence properties of 1 and 2 were also studied.

[Na(THF)_（2）(μ_（2）-η^(5)-Cp)(η^(5),η^(5),η^(1)- Cp_(3)Yb)(THF)]_(n):The synthesis and X-ray structure of an anionic organolanthanide polymer formed via self-assembly

Cp2Yb·2THF reacts with CpNa in 1:1 molar ratio in THF at 40℃ for 2 h, and the in situ generated ani-onic divalent complex NaYbCp3(THF)n reacts further with an excess of CpH at 40℃ for 48 h, after work-up, affording the trivalent anionic ytterbium complex [Na(THF)2(μ2-η5-Cp) (η5,η5,η1-Cp3Yb)(THF)]n (1) by oxidation reaction of Cp2Yb with CpH. Crystal structure determination reveals that com-plex 1 has one-dimension polymeric chains of distinct Na(THF)2(μ2-η5-Cp)(η5,η5,η1-Cp3Yb)(THF) units, which were formed by the coordination of the bridging Cp ligand with Cp3Yb·THF and Na(THF)2 in η5,η5 mode via self-assembly.

Preparation and Structure of[(C_(5)H_(4)Me)_(2)Sm(THF)(DME)][BPh_(4)]

Reaction of (C5H4Me)3Sm with AgBPh4 in THFDME provides a route to cationic organosamarium complex of . The product is characterized by elemental analysis, infrared spectra and Xray crystallography. Crystallographic data are as follows: formula C88H104B2O6Sm2, FW=158021, monoclinic, space group P21/a, a=17911(4), b=21368(4), c=20894(7) nm, =10177(2), V=7828(3) nm3, Z=4, Dc=1341 gcm-3, (Mo K)=1541 cm-1, F(000)=3256, R=0040, RW=0051. Two centroids of the cyclopentadienyl groups and three oxygen atoms around a samarium atom form a distorted trigonal bipyramid.

4-硝基氮氧化吡啶-2-甲酸构筑的镧、镨配合物的合成、晶体结构及荧光性质

选择刚性有机化合物4-硝基氮氧化吡啶-2-甲酸(POA)作为配体,与稀土金属La(III)、Pr(III)反应,合成了2个一维配位聚合物。X射线单晶衍射结果表明:配合物1的分子式为{[La(POA)_(3)H_(2)O]·CH_(3)OH}n,属于单斜晶系,空间群是P2_(1)/c。该晶胞参数分别为a=1.7568 nm,b=0.6636 nm,c=2.0486 nm,α=90°,β=96.96°,γ=90°,V=2.3707 nm^(3),M_(r)=738.28。配合物2的分子式为{[Pr(POA)_(3)H_(2)O]·H_(2)O}n,属于单斜晶系,空间群是P2_(1)/c。该晶胞参数分别为a=1.7578 nm,b=0.6569 nm,c=2.0467 nm,α=90°,β=97.20°,γ=90°,V=2.3448 nm^(3),M_(r)=726.25。两个配合物的配位单元组成和结构相似,中心离子都处于稍变形的三帽三棱柱的配位环境中。通过红外光谱、紫外光谱、热重分析仪和荧光光谱仪对两个配合物的性质进行表征。荧光分析表明,配体和配合物均有较强的荧光性能。

一个新颖的三维异核锑(Ⅲ)-镨(Ⅲ)配合物[Sb_2-μ_4-(EDTA)_2Pr(H_2O)_5]NO_3·4H_2O的合成、晶体结构及热分解研究

合成了锑-镨与乙二胺四乙酸形成的新颖三维配合物[Sb2-μ4-(EDTA)2Pr(H2O)5]NO3·4H2O,用元素分析、红外光谱、热分析及X射线单晶衍射法等进行了组成和结构表征.结果表明该配合物属正交晶系,空间群Pnn2;晶胞参数:a=1.07031(2)nm,b=2.30805(4)nm,c=0.72343(2)nm,V=1.78711(7)nm3,Z=2,Dc=2.202g/cm3,F(000)=1164,μ=2.955mm-1,GOF=1.000,最终偏离因子R1=0.0203,wR2=0.0545[I>2σ(Ⅰ)].在标题化合物中,每个镨(Ⅲ)离子的配位数为9,与五个水分子中的五个氧原子和四个羧基氧原子配位,形成三帽三角棱柱空间配位多面体.锑(Ⅲ)与EDTA离子中的四个氧原子和两个氮原子配位,在赤道平面上有一孤对电子.同时讨论了配合物的热分解过程.

烟酸镨Pr_2(C_5H_4NCOO)_6(H_2O)_4的晶体结构

从ＬｎＡｌａＮＡ溶液（Ｌｎ＝Ｎｄ，Ａｌａ＝Ｌ丙氨酸；ＮＡ＝烟酸）中得到烟酸镨晶体，并用四圆Ｘ射线衍射技术重新测定其结构．配合物为二聚体结构，属单斜晶系，Ｐ２１／ｃ空间群，晶胞参数：ａ＝９．７１２５（９），ｂ＝１２．０４９８（１１），ｃ＝１７．１５１（２），β＝９２．６８８（６）°，Ｖ＝２００５．１（３）３，Ｚ＝２，Ｄｃ＝１．８００ｇ／ｍＬ．其配位数为８，配位多面体为四方反棱柱．本文讨论了稀土烟酸配合物结构规律性．

1-甲基-1-丙基-3-丁烯基环戊二烯基钆配合物的合成和晶体结构分析

用X-射线晶体结构衍射法测定了[C_5H_4C(CH_3)(C_3H_7)CH_2CH=CH_2]Gd(OH)Cl·2MgCl_2·4 THF的晶体结构。它属三斜晶系,空间群为P,a=1.2757(3),b=1.3571(3),c=1.3725(3)nm,α=69.22(3),β=84.91(3),γ=63.48(3)°,V=1.929(1)nm^3,Mr=862.75,D_X=1.423g/cm^3,μ=2.0832mm^(-1),F(000)=848,Z=2,R=0.096,wR=0.113(I≥3σ(I))。分子中Gd原子的配位数为8,形成一个严重扭曲的八面体结构;两个Mg原子的配位情况相似,它们的配位数都是6,构成两个扭曲的八面体。这三个八面体通过三个共用平面联接。

苯磺酰β-丙氨酸镨配合物的合成及晶体结构

合成了配合物{[Pr2 L6 (H2O)4]?H 2O}n (L = 苯磺酰b-丙氨酸), 并通过单晶X射线衍射确定了晶体结构。化合物(C27H41.21N3O17.6PrS3)属单斜晶系, 空间群P21 /n, 晶胞参数:a = 9.412(1), b = 18.019(2), c = 22.522(4) , b = 100.43(1), Z = 4, Mr = 926.59, Dc = 1.638 g/cm3, V = 3756.3(8) 3, F(000) = 1888, m = 1.540 mm1 。PrⅢ离子为9配位的单帽四方反棱柱结构, 羧基氧原子与镨原子间存在3种配位方式, 镨原子之间通过2种类型的羧基连接使配合物分子呈无限链状结构。

〔C_5H_4C(CH_3)_2CH_2CH=CH_2〕Sm(OH)Cl·2MgCl_2·4THF的晶体结构分析

用Ｘ－射线晶体结构衍射法测定了〔Ｃ５Ｈ４Ｃ（ＣＨ３）２ＣＨ２ＣＨ＝ＣＨ２〕Ｓｍ（ＯＨ）Ｃｌ·２ＭｇＣｌ２·４ＴＨＦ的晶体结构。它属三斜晶系，空间群为Ｐ１，ａ＝１０．７７３（２），ｂ＝１２．８３６（３），ｃ＝１５．４７８（３），α＝１１１．４６（３），β＝１０７．７１（３），γ＝９２．５４（３）°，Ｖ＝１８６８（１）３，Ｍｒ＝８２７．９１，Ｄｘ＝１．４７２ｇ／ｃｍ３，μ＝２．０００６ｍｍ－１，Ｆ（０００）＝８４０，Ｚ＝２，Ｒ＝０．０４１，ｗＲ＝０．０５０（Ｉ≥３σ（Ｉ））。分子中Ｓｍ原子的配位数为８，形成一个严重扭曲的八面体结构；２个Ｍｇ原子的配位情况相似，它们的配位数都是６，分别构成２个扭曲的八面体。

[C_5H_4C(CH_3)(C_3H_7)CH_2CH=CH_2]NdMg_2(μ_3-OH)(μ_3-Cl)(μ_2-Cl)_3(THF)_4Cl的合成和晶体结构分析

用Ｘ－射线衍射法测定了［Ｃ５Ｈ４Ｃ（ＣＨ３）（Ｃ３Ｈ７）ＣＨ２ＣＨ＝ ＣＨ２］ＮｄＭｇ２（μ３－ＯＨ）（μ３－Ｃｌ）（μ２－Ｃｌ）３（ＴＨＦ）４Ｃｌ的晶体结构。它属三斜晶系，空间群为Ｐ１－ ，ａ＝ １２．６９８（３）， ｂ＝ １３．６１６（３）， ｃ＝ １３．７１２（３）， α＝ ６８．９１（３）， β＝ ８４．３４（３）， γ＝ ６３．０７（３）°， Ｖ＝ １９６６（１）３， Ｍｒ＝ ８４９．７４， Ｄｘ＝ １．４１２ ｇ·ｃｍ － ３， μ＝ １．７２９７ ｍ ｍ － １， Ｆ（０００）＝ ８４０， Ｚ＝ ２， Ｒ＝ ０．０７３， ｗ Ｒ＝ ０．０８６（Ｉ≥３σ（Ｉ））。分子中Ｎｄ（Ⅲ）原子的配位数为八，形成一个严重扭曲的八面体结构。两个Ｍｇ 原子的配位情况相似，它们的配位数都是六，构成两个扭曲的八面体。