N-对R苯基氮杂15冠5八钼多酸钠超分子配合物的合成与结构

为研究大环化合物对客体分子的选择性, 合成了通式为[NaL(Et2O)]2Na2Mo8O26的三种新型N-对R苯基氮杂15冠5八钼多酸钠超分子配合物(其中L分别为: N-苯基氮杂15冠5、N-对氯苯基氮杂15冠5和N-对甲苯基氮杂15冠5), 进行了元素分析, 红外光谱与核磁共振等结构参数的表征, 对R基为CH3的标题配合物作了X射线四圆衍射测定, 该晶体属单斜晶系, 空间群为P21/a,a=1.4590(4)nm, b=1.3817(3)nm, c=1.7639(5)nm, β=112.67(2)°, V=3.281(1)nm^3, Mr=2021.3, Dc=2.11g/cm^3,μ=2.37mm^-^1, F(000)=2048, R=0.045和Rw=0.057, 与[Na.(DB18C6)(CH3OH)M6O19和[Na(DB24C8)]2M6O19进行比较,结果表明: 大环化合物不仅对客体金属离子有分子识别性, 而且对与之抗衡的多酸阴离子也具有影响。     

一种具有梯状链结构有机模板硫酸铽的合成、结构表征以及荧光性质

本文采用溶剂热法合成了一种具有梯状链结构新的有机模板硫酸铽盐:(C2H8N)[Tb(SO4)2.H2O](1),并通过X-射线衍射、红外、热重及元素分析对其进行了表征。该晶体属于单斜晶系,P21/n空间群。其中a=0.568 1(3)nm,b=1.972 7(10)nm,c=0.862 7(4)nm,β=90.658(6)°,V=0.966 7(8)nm3,Z=4。化合物1的骨架结构由TbO8多面体和SO4四面体构成。S(1)和S(2)与Tb(1)相连接,通过3个S-O-Tb连接构成双链,而相邻的双链通过μ3-O(O5)连接形成一个新的梯状链。     

Cobalt-lanthanide coordination polymers constructed with metalloligands: a ferromagnetic coupled quasi-1D Dy3+ chain showing slow relaxation

Four types of cobalt-lanthanide heterometallic compounds based on metalloligand Co(2,5-pydc)(3) (3-) (2,5-H(2)pydc=pyridine-2,5-dicarboxylate acid), [Ln(2)Co(2)(2,5-pydc)(6)(H(2)O)(4)](n) 2n H(2)O (1) (Ln=Tb, Dy for 1 a, 1 b respectively), [Tb(2)Co(2)(2,5-pydc)(6)(H(2)O)(4)](n)3n H(2)O (2), [Tb(2)Co(2)(2,5-pydc)(6)(H(2)O)(9)](n)4n H(2)O (3), and [LaCo(2,5-pydc)(3)(H(2)O)(2)](n)2n H(2)O (4) have been synthesized. Compound 1 has a layer structure with well-isolated carboxylate-bridged Ln(3+) chains, compound 2 is a three-dimensional (3D) porous network with Tb(3+) chains that are also well isolated and carboxylate bridged, 3 is a layer structure based on dinuclear units, and 4 is a 3D network with boron nitride (BN) topology. DC magnetic studies reveal ferromagnetic coupling in all the carboxylate-bridged Ln(3+) chains in 1 a, 1 b, and 2. Compared to the silence of the out-of-phase ac susceptibility of 2, above 1.9 K the magnetic relaxation behavior of both 1 a and 1 b is slow like that of a single-chain magnet.     

SYNTHESIS, STRUCTURE AND PROPERTIES OF Na_3[V_2O_3(nta)_2]·5H_2O

<正> Compound Na3 [V2O3 (nta )2 ]·5H2O (1) (ntaH3 = N (CH2CO2H)3) has been prepared by reduction of a mixture of (NH4)2[VO(O2)2Cl] and H3(nta) in H2O with Na2S2O4. The compound crystallizes in the triclinic system, space group P1 with Mr = 685. 2, a = 11. 050(6), b=12. 179(4), c=9. 792 (3)A,α=111.71(2),β= 98. 23(3), γ= 89. 36(2)°, Z=2, V = 1210. 5A3,λ(MoKa) = 0. 71069 A, F(000) = 694 and DC = 1. 880g/cm3. The structure was solved by direct methods and refined by full-matrix least squares to final R and Rw values of 0. 055 and 0. 065, respectively.The structure of the anion can be considered as two [VO(nta)] fragments connected by one μ2-O atom. Each vanadium atom in the fragment is coordinated by one vanadyl oxygen atom, one bridging-oxygen atom, three oxygen atoms and one nitrogen atom from (nta) ligand in a distorted octahedral geometry. In this paper, we have studied the conversion of compound 1 to mononuclear compound Na2[VO(O2) (nta)]·5H2O (2) by oxidation with hydrogen peroxide, as well as thei     

p-Hydroquinone-metal compounds: synthesis and crystal structure of two novel VV-p-hydroquinonate and VIV-p-semiquinonate species

Reaction of the p-hydroquinone derivative H2Na4bicah.4H2O with either VIVOSO(4).3H2O and NaVVO3 in equivalent quantities or with NaVVo3 yields the tetranuclear VIVO2+ macrocycle-semiquinonate compound Na6[(VIVO)4-(mu2-O)2[mu2-bicas.(-5)-N,O,O,O]2].Na2SO(4).20H2O (1.Na2SO(4).20H2O) and the dinuclear cis-VVO2(+)-hydroquinone species Na4[(VVO2)2[mu2-bicah(-6)-N,O,O,O]].11H2O (2.11H2O) respectively. Compounds 1.Na2SO(4).20H2O and 2.11H2O were characterized by X-ray structure analysis and ab initio calculations.     

(enH_2)_4Na_4H_3[(VO)_(12)O_6B_(18)O_(42)]·8H_2O的水热合成和晶体结构

在水热的条件下合成了多钒硼酸盐(enH2)4Na4H3[(VO)12O6B18O42]8H2O, 化学式为C8H59B18N8Na4O68V12 (Mr=2253.45), 用单晶X射线衍射方法测定了它的结构, 该晶体属单斜晶系, P21/n空间群, 晶胞参数为a = 13.8989(4), b = 16.1954(5), c = 14.4520(4) ?β = 94.7490(5), V= 3241.95(16) ?, Z = 2, Dc = 2.308 g/cm3, ?= 1.819mm-1, F(000) = 2234, 4798个可观察衍射点(I > 2s(I)), 最终结构精修到偏离因子R = 0.0449, wR = 0.1163, S = 0.996。在该化合物的结构中, V12B18簇是由环状的B18O42通过18个B(μ3-O)V键被2个V6O18环夹在中间组成的, V12B18簇通过4个Na+与相邻的簇相连, 形成二维网状结构, 孔道尺寸为6.109×10.562 拧?     

High-pressure preparation,crystal structure,and properties of alpha-(RE)2B4O9 (RE=Eu,Gd, Tb,Dy): oxoborates displaying a new type of structure with edge-sharing BO4 tetrahedra

High-pressure/high-temperature conditions of 10 GPa and 1150 degrees C were used to synthesize the new rare-earth oxoborates alpha-(RE)(2)B(4)O(9) (RE=Eu, Gd, Tb, Dy) in a Walker-type multianvil apparatus. Single-crystal X-ray structure determination of alpha-(RE)(2)B(4)O(9) (RE=Eu, Gd, Tb) revealed: C2/c, Z=20, alpha-Eu(2)B(4)O(9): a=2547.9(5), b=444.3(1), c=2493.8(5) pm, beta=99.82(3) degrees, R1=0.0277, wR2=0.0693 (all data); alpha-Gd(2)B(4)O(9): a=2539.0(1), b=443.3(1), c=2490.8(1) pm, beta=99.88(1) degrees, R1=0.0457, wR2=0.0643 (all data); alpha-Tb(2)B(4)O(9): a=2529.4(1), b=441.6(1), c=2484.3(1) pm, beta=99.88(1) degrees, R1=0.0474, wR2=0.0543 (all data). The isotypic compounds exhibit a new type of structure that is built up of BO(4) tetrahedra to form a network that incorporates the rare-earth cations. The most important feature is the existence of the new structural motif of edge-sharing BO(4) tetrahedra next to the known motif of corner-sharing BO(4) tetrahedra, which is realized in the presented compounds alpha-(RE)(2)B(4)O(9) (RE=Eu, Gd, Tb, Dy) for the second time. Furthermore, we report the temperature-resolved in-situ powder-diffraction measurements, DTA, IR/Raman spectroscopic investigations, and magnetic properties of the new compounds.     

Sodium Ion-linked Waugh Polyanion with a 4,4-Connected Layered Structure

A new polyoxometalate comPOund formulated as Na2（C3H5N2）4[MnMo9O32]·2H2O 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group C2/c, with a = 16.076（2）, b = 14.6488（19）, c = 18.767（2）A ,β = 108.6030（10）°, V = 4188.6（9）A^3, C12H24MnMo9NsNa2O34, Mr = 1788.77, Dc = 2.837 g/cm^3,μ（MoKa） = 3.024 mm^-1, F（000） = 3396, Z = 4, the final R = 0.0270 and wR = 0.0605 for 3829 observed reflections （I 〉 2σ（I））.     

Syntheses, thermal stability, and structure determination of the novel isostructural RBa3B9O18 (R = Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb)

A novel borate compound YBa(3)B(9)O(18) has crystallized in a melt of BaYB(9)O(16). Single-crystal X-ray diffraction measurements reveal that YBa(3)B(9)O(18) adopts a hexagonal space group P6(3)/m with cell parameters of a = 7.1761(6) A and c = 16.9657(6) A. The structure is made up of the planar B(3)O(6) groups parallel to each other along the (001) direction, regular YO(6) octahedra, and irregular BaO(6) and BaO(9) polyhedra to form an analogue structure of beta-BaB(2)O(4). A series of isostructural borate compounds RBa(3)B(9)O(18) (R = Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb) were prepared by powder solid-state reactions. The DTA and TGA curves of YBaB(9)O(16) show an obvious weight loss at about 955 degrees C associated with a decomposition into YBO(3), B(2)O(3), and YBa(3)B(9)O(18) due to its incongruent melting behavior. The DTA and TGA curves of YBa(3)B(9)O(18) show that it is chemically stable and a congruent melting compound. A comparison of the structures of YBa(3)B(9)O(18) and beta-BaB(2)O(4) is presented.     

Synthesis and Structure of K_3Na_3〔MnMo_9O_(32)〕·6H_2O

1INTRODUCTIONHeteroPOlymolybdatesareknownwithaverywiderangeofmetalionsithetypeandstabilityoftheclustersshowdependenceonboththeheteroatomandPH"'.TheknownheteroPOlymolybdateswhichincludemanganese(1)ormanganese(IV)havebeenreported.Afewofhetercrg-molybdateanionswiththemanganese(IIV)andnickel(IV)formsarecharacterizedandisostructural[2).Thesehigheroxidationstatespecieshavebeenpreparedpreviouslybyoxidationoflower--valentspecieswithPOwerfuloxidant,suchasPeroxydisulfateorPeroxymonosulfurica…     

1D molecular ladder of the ionic complex of terbium-4-sebacoylbis(1-phenyl-3-methyl-5-pyrazolonate) and sodium dibenzo-18-crown-6: synthesis, crystal structure, and photophysical properties

On the basis of the novel heterocyclic beta-diketone, 4-sebacoylbis(1-phenyl-3-methyl-5-pyrazolone (H 2SbBP), three new lanthanide complexes Tb 2(SbBP) 3(H 2O) 2 ( 1), Gd 2(SbBP) 3(H 2O) 2 ( 2), and [Tb(SbBP) 2] [Na(DB18C6)H 2O] ( 3) have been synthesized and characterized by various spectroscopic techniques. The single-crystal X-ray diffraction analysis of 3 reveals that the complex crystallizes in the monoclinic space group C2/ c with a = 25.300(6) A, b = 19.204(7) A, c = 15.391(3) A, beta = 93.17(3) degrees , and V = 7466(4) A (3). The crystal structure of 3 is heterodinuclear and features a Tb (3+) center surrounded by two tetradentate bispyrazolone ligands in a somewhat distorted square-antiprismatic geometry. The Na (+) coordination environment is distorted hexagonal pyramidal and involves six oxygen atoms furnished by DB18C6 and one oxygen atom from a water molecule. The X-ray diffraction study of 3 also revealed an interesting 1D molecular ladder structure based on C-H/pi, intra- and intermolecular hydrogen-bonding interactions. The photophysical properties of 1 and 3 in solid state have been investigated, and the quantum yields and (5)D 4 lifetimes were found to be 4.82 +/- 0.01% and 18.13 +/- 0.82% and 1.11 +/- 0.01 and 2.82 +/- 0.02 ms, respectively.     

Hydrothermal Synthesis and Crystal Structure of a New Hexa-cobalt-containing POM

A new compound Na3H3[Co（en）3]2[Co4（H2O）2（PW9O34）2]·11H2O 1 （en = ethylenediamine） has been synthesized under hydrothermal conditions and characterized by IR, TGA, and single-crystal X-ray diffraction analysis. Crystal data： monoclinic, space group C21c, a = 26.336（5）, b = 18.135（2）, c = 22.751（4）A, β = 123.039（7）° and Z = 4. X-ray crystallographic study on compound 1 reveals that it includes a Weakley-type sandwich polyoxoanion [Co4（H2O）2（PW9O34）2]^10-, two complex ions [Co（en）3]^2＋, three Na^＋ ions （one Na（1） and two Na（2））, and eleven crystallographic water molecules. The sandwich polyoxoanions are linked by Na2 to form 2D layers parallel to the （100） plane, and these layers are further connected by Nal along the α-axis to generate a 3D structure.     

New Layered Polyborates Cs(2)M(2)B(10)O(17) (M = Na, K)

The polyborates Cs(2)M(2)B(10)O(17) (M = Na, K) have been prepared and their structures determined by single-crystal X-ray diffraction methods. They crystallize in the monoclinic space group C2/c (Z = 8) with unit-cell parameters a = 21.643(3) ?, b = 6.558(2) ?, c = 11.072(2) ?, beta = 105.43(1) degrees, V = 1514.8(6) ?(3) for the Na compound and a = 22.547(9) ?, b = 6.614(2) ?, c = 11.288(4) ?, beta = 103.25 degrees, V = 1638.3(8) ?(3) for the K analogue. The new structural type contains a 2-dimensional borate matrix that is built from a complete condensation of the ring system B(5)O(11). The Cs atoms reside within the borate matrix, and the Na (K) atoms are placed between the thick Cs borate sheets.     

[Cu(en)_2]~(2+)修饰的二维仲钨酸化合物:[{Na_3(H_2O)_(10)}_2H_2{Cu(en)_2(H_2W_(12)O_(42))}]·16H_2O(英文)

利用水热合成法制备了一种基于[Cu(en)2]2+修饰的仲钨酸化合物:[{Na3(H2O)10}2H2{Cu(en)2(H2W12O42)}].16H2O(en=乙二胺)(1),借助元素分析、X射线单晶衍射分析I、R、UV、热分析和X射线光电子能谱对这种化合物进行了结构和性质研究.化合物(1)属于三斜晶系,P-1空间群.晶胞参数为:a=1.183 2(5)nm,b=1.296 0(6)nm,c=1.416 9(6)nm,α=63.348 0(10)°,β=82.844 0(10)°,γ=68.907 0(10)°,V=1.810 0(14)nm3,Z=1,R1[I2σ(I)]=0.024 7,wR2[I2σ(I)]=0.058 2.化合物(1)通过仲钨酸阴离子,铜离子和[Na3(H2O)10]3+三核簇形成了新型的二维层状结构.     

Structures and magnetism of two novel heptanuclear lanthanide-centered trigonal prismatic clusters: [LnCu6(mu 3-OH)3(HL)2(L)4](ClO4)2.25H2O (Ln = La, Tb; H2L = iminodiacetic acid)

The new heteronuclear iminodiacetic acid (H2L) complexes [LnCu6(mu 3-OH)3(HL)2(L)4](ClO4)(2).25H2O with Ln = La (1) and Tb (2) have been prepared in aqueous solution and characterized by single-crystal X-ray diffraction to be isomorphous (crystallographic data for 1 and 2: hexagonal, P63/m; a = b = 12.6425(14) A, c = 24.541(5) A, Z = 2 (1); a = b = 12.5802(9) A, c = 24.285(4) A, Z = 2 (2)). Ln3+ was found to be located in the center of the trigonal prismatic cage formed by six Cu2+ ions, with a tricapped trigonal prismatic coordination environment of nine O atoms. The magnetic properties of complexes 1 and 2 have been studied. The results indicate the presence of ferromagnetic couplings between Tb3+ and Cu2+ in compound 2.     

新颖的咪唑官能化夹心型钨铋酸盐超分子化合物的合成与晶体结构

在常规条件下合成了一个新颖的超分子化合物Na8H[{Na(H2O)}3{Mn(C3H4N2)}3(BiW9O33)2]·32H2O, 通过X射线单晶结构分析、红外光谱及元素分析对该化合物进行了表征. 结果表明, 该化合物属六方晶系, P6(3)/m空间群. 晶胞参数a=1.394 8(4) nm, b=1.394 8(4) nm, c=3.348 6(19) nm, γ=120°, V = 5.641(4) nm3, Z=12. 该化合物是以α-B-BiW9钨铋酸盐为基本构筑单元的夹心结构化合物. 夹层中心3个Mn2+分别与3个咪唑分子配位形成无机-有机杂化材料. 3个[{Na(H2O)}3{Mn(C3H4N2)}3(BiW9O33)2]9-多阴离子结构基元利用氢键(非典型氢键)沿ab面构筑成具有三角形空穴的二维层状骨架结构. 这种二维层状结构利用氢键作用沿c轴方向交错排列, 形成了含有一维六边形孔道的三维超分子结构.     

穴状化合物(NH_4)_(16)H_2[NaSb_9W_(21)O_(86)]·15.5H_2O的合成及晶体结构(英文)

利用Sb2O3,Na2WO4合成了一个巨型的穴状化合物(NH4)16H2[NaSb9W21O86].15.5H2O.晶体衍射数据显示,该化合物属于六方晶系,P6-2c空间群,a=b=1.78025(9)nm,c=2.2510(2)nm,α=β=90(9)°,γ=120(2)°,V=6.1783(7)nm3,Z=2,Dc=3.722Mg/m3,F(000)=6086,μ=21.494mm-1,R1=0.0365,wR2=0.0871[I≥2σ(I)].晶体解析表明,该化合物多阴离子[NaSb9W21O86]18-由3个[SbW7O24]3-亚单元和2个环形的[Sb3O7]5-基团连接形成双环孔穴,一个Na+阳离子通过配位键作用嵌入该空穴内.整个穴状物阴离子呈涡轮状结构,3个[SbW7O24]3-亚单元作为3个叶片.     

稀土亚磷酸盐GdxTb2-x（HPO3）3（H2O）2（0≤x≤2）的微波合成、表征与性质研究

利用微波辅助合成法,成功地合成出一系列新颖的稀土亚磷酸盐GdxTb2-x(HPO3)3(H2O)2(0≤x≤2).X-射线粉末衍射分析结果表明,它们为同构的化合物.对Gd2(HPO3)3(H2O)2进行X-射线单晶衍射分析得出,该化合物结晶于P21/c空间群,晶胞参数为a=6.9124(6),b=12.8891(12),c=12.3692(11),β=100.1520(10)°.Gd2(HPO3)3(H2O)2是由GdO7多面体,GdO8多面体和[HPO3]假四面体通过共用氧原子相互连接而成的三维骨架.Gd2(HPO3)3(H2O)2和Tb2(HPO3)3(H2O)2的荧光光谱分别显示Gd3+和Tb3+的特征发光.Gd/Tb掺杂的样品中存在Gd3+-Tb3+的能量传递,它们的发光显示Tb3+的绿光发射(5D4→7F3-6),并且5D4→7F3跃迁的强度随着Tb3+掺杂量的增大而增强,这表明Gd2(HPO3)3(H2O)2引入不同浓度的发光中心Tb3+之后可以作为绿光发光材料.磁性研究表明,Gd2(HPO3)3(H2O)2中存在极弱的反铁磁相互作用.     

Synthesis and Crystal Structure of the Heteropolymate Compound Na3H2[Ce3(H2O)18Bi2W22O76]·23H2O

A Bi(Ⅲ) contained heteropolymate compound Na3H2[Ce3(H2O)18Bi2W22O76] (23H2O 1 has been synthesized. It crystallizes in the triclinic system, space group P with a = 14.370(3), b = 17.113(3), c = 24.764(5) A, α = 74.33(3), β = 77.20(3), γ = 65.29(3)o, V = 5285.3(18) A3, Z = 2, Mr = 6908.66, Dc = 4.341 g/cm3, F(000) = 6042, μ(MoKσ) = 28.543 mm-1, R = 0.0604 and wR = 0.1659 for 15788 reflections with I > 2σ(I). The structure analysis revealed that in the anionic framework of the title compound the [Bi2W22O76]14- anions are connected by Ce3+ and Na+ cations into a three dimensional network.     

Crystal Structure and Characterization of a Novel 2D Layered Compound Assembled from Paradodecatungstate Clusters

A novel 2D layered compound （H4HMTA）2（H3O）2{Na2（H2O）6（H2W12O42） }C12-11H2O （HMTA = hexamethylenetetraamine） has been synthesized and characterized by elemental analyses, IR, UV-Vis and X-ray diffraction. C12H74CI2N8Na2O61W12 （Mr = 3629.87） crystallizes in the triclinic system, space group P1 with a = 10.5518（2）, b = 12.1837（2）, c = 14.3088（2） A, α = 112.9470（10）, β = 93.1310（10）, γ= 106.1530（10）°, V = 1599.20（5）A3 Dc = 3.769 g.cm^-3, Z = 1, μ（MoKα） = 21.705 mm^-1, F（000） = 1634, the final R = 0.0287 and wR = 0.0686 for 5846 observed reflections with I 〉 2σ（I）. The 2D layered network is assembled from paradodecatungstate clusters linked by simple sodium-oxo bridging groups. The compound exhibits electrocatalytic activities toward both reduction and oxidation of nitrite.