Hydrothermal Syntheses, Structure Characteristics and Magnetic Properties of a Series of New Molybdenum Arsenates Based on {(As3O3)2(Mo6O18)(MO6)}(M = Ni, (1); Co, (2); Zn, (3))

Three new polyoxometalates K2[H2（As3O3）2（Mo6O18）（NiO6）]？H2O （1）, K2[H2-（As3O3）2（Mo6O18）（CoO6）]？H2O （2） and [Zn（H4,4？-bpy）2（H2O）4][（As3O3）2（Mo6O18）（ZnO6）]？4H2O （3） （4,4？-bpy = 4,4？-bipyridine） have been synthesized under hydrothermal conditions and characterized by IR, elemental analyses, XPS and single-crystal X-ray diffraction analyses, respectively. Compound 1 represents a new 3D framework structure constructed from polyoxoanion [（As3O3）2（Mo6O18）（NiO6）]4- via covalent bond. Compound 2 has an identical structure with 1. Compound 3 represents a new 2D layer structure constructed from transition metal coordination cations [Zn（H4,4？-bipy）2（H2O）4]4＋, lattice water molecules and polyoxoanions [（As3O3）2- （Mo6O18）（ZnO6）]4- via multi-point N–H？？？O and O–H？？？O hydrogen bonding interactions. Crystal data： for 1, cubic, space group Pa-3, a = 15.0022（8） ？, V = 3376.5（3） ？3, Z = 24; for 2, cubic space group Pa-3, a = 15.1596（10）, V = 3483.88 ？3, Z = 24; for 3, monoclinic, space group C2/m, a = 19.699（4）, b = 14.223（3）, c = 9.1455（18） ？, β = 106.80（3）o, V = 2453.0（9） ？3, Z = 8. In addition, the magnetic behaviors for compounds 1 and 2 have been investigated.

Hydrothermal Synthesis and Crystal Structure of a New Sandwich-type Molybdenum Phosphate

The crystal structure of the title compound, [enH2][Fe{MoⅤ6O12(OH)3(HPO4)- (H2PO4)3}2]6en6H2O (en = H2NCH2CH2NH2), hydrothermally synthesized from a mixture of Na2MoO42H2O, Fe2(SO4)3, H3PO4, H2N(CH2)2NH2 and water, has been determined by single- crystal X-ray diffraction. The crystal is of triclinic, space group P?with a = 11.9014(1), b = 13.4246(2), c = 13.8719(2) , a = 87.465(1), b = 69.981(1), g = 64.960(1)? V = 1873.46(4) 3, Z = 1, Mr = 2997.89, F(000) = 1466, m = 2.427 mm-1 and Dc = 2.657 g/cm3. The final R = 0.0404 for 5570 observed reflections (I > 2s(I)). The structural analysis reveals that each cluster anion contains two coplanar {Mo6} rings of six edge-sharing Mo(O5OH) octahedra, and the two {Mo6} rings are linked together through one octahedral FeⅡ ion to generate a sandwich-type cluster with rigorous () symmetry. Moreover, these clusters are further linked into a three-dimensional frame- work by hydrogen bonds.

Hydrothermal Synthesis and Crystal Structure of [H_4As_8V_(14)O_(42)(H_2O)]·6H_2O

The title compound [H4As8V14O42(H2O)]6H2O 1 has been synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction analysis. It crystallizes in trigonal, space group R3c with a = b = 36.447(6), c = 21.485(5) ? V = 24717(8) 3, Z = 18, Mr = 2114.66, Dc = 2.557g/cm3, F(000) = 17928, m = 7.149 mm-1, R = 0.0792 and wR = 0.1265. The [H4As8V14O42- (H2O)] cluster consists of fourteen VO5 square pyramids linked by four As2O5 handle-like units.

Hydrothermal Synthesis, Crystal Structure,Thermal Stability and Photophysical Property of a Novel Zinc Complex with Mixed Ligands

A novel metal-organic coordination complex [Zn（CHIP）（AIC）]n （1, CHIP = 2-（4- chlorophenyl）-lH-imidazo[4,5-f][1,10]phenanthroline, A1C = 5-amino-isophthalic acid） has been synthesized by hydrothermal reactions and characterized by elemental analysis, thermogravimetric （TG） analysis, infrared spectrum （IR） and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a = 18.259（5）, b = 17.191（4）, c = 16.371（4） A, V= 4717（2） A3, C27H16C1NsOnZn, Mr= 575.29, Dc = 1.620 g/cm3, p（MoKa） = 1.202 mm-1, F（000） = 2335, Z = 8, the final R = 0.032 and wR = 0.074 for 4723 observed reflections （I 〉 2σ（I））. Single-crystal X-ray diffraction reveals that 1 exhibits one-dimensional （1D） double chains, which are linked by H-bond intersections into a 2D structure. TG analysis shows clear weight loss due to the decomposition of different ligands. The luminescent properties for the ligand and complex 1 were also studied.

Hydrothermal Syntheses, Crystal Structures and Luminescence Properties of Zn(Ⅱ) and Cu(Ⅱ) Complexes Based on 2,2'-((Sulfonylbis(4,1-phenylene))bis(oxy))diacetic Acid

The 2,2'-((sulfonylbis(4,1-phenylene))bis(oxy))diacetic acid(H2L) and 4,4'-bipyridine(4,4'-bipy) are employed as organic ligands to react with metal salts to obtain two new metal-organic frameworks(MOFs), namely [M2L2(4,4'-bipy)](M = Zn(1), Cu(2)). They have been successfully synthesized under hydrothermal conditions. Single-crystal X-ray diffraction reveals that two complexes are isostructural and crystallize in orthorhombic system with space group Pbcn. All L^(2-) ligands bridge metal ions to form an infinite 1D Z-shaped chain along the a axis. Then through 4,4'-bipy, contiguous Z-shaped chains are linked to form a 2D layer structure. The luminescent studies of the H2L ligand and complex 1 in the solid state and thermogravimetric analyses(TGA) of two complexes are investigated.

Hydrothermal Synthesis and Structure of a New Molybdenum Phosphate: (NH_3CH_2CH_2NH_3)_(2.5)[Mo_5O_(15)(PO_4) (HPO_4)]·7.5H_2O

The title compound (C5N5H41P2Mo5O30.5) was synthesized under hydrothermal condition and its crystal structure was determined by X-ray diffraction. It belongs to triclinic system, space group P , with a=9.9645(6), b=10.8666(7), c=15.814(1)? α=71.482(3), β=88.528(2), γ=78.448(2)°, V=1589.4(2)3, Dc=2.510g/cm3, Z=2,μ=2.138mm-1,λ(MoKα) = 0.71073 ? F(000)=1180. The final R and wR were 0.0396 and 0.1052 for 6626 observed reflections with I ≥2σ(I), respectively. The result of the structure analysis indicates that the [Mo5O15(PO4) (HPO4)]5- anion in the title compound consists of five edge-sharing or corner-sharing MoO6 octahedra and two corner-sharing PO4 tetrahedra. Each MoO6 octahedron adopts distorted octahedral geometry.

Hydrothermal Synthesis and Structure of a Novel Molybdenum Phosphate: Na_4(H_3O) [Na(HPO_4)_2(PO_4)_4Mo_(18)O_(49)]·16H_2O

The title compound Na5H37P6Mo18O90 1 (Mr=1658) was synthesized under hydrothermal condition and its crystal structure was determined by X-ray diffraction. It crystallized in the monoclinic system, space group P21 with a =14.957(1), b =16.535(1), c = 16.159(1)?β=108.586(2)°, V=3787.85?, Dc =3.040g/cm3, Z=2,μ(MoK)=3.17mm-1, F(000)=3242. The final R and wR are 0.0500 and 0.1535 for 6643 observable reflections with I≥2?I), respectively. The result of structure analysis indicates that [Na(HPO4)2(PO4)4-Mo18 O49]5-anions 2 in 1 has the symmetry of C2V, in which each MoVIO6 octahedron is connected to adjacent PO4 tetrahedra through corner-sharing and to adjacent octahedra through edge-sharing or corner-sharing.

Hydrothermal Synthesis and Structure of a Novel Binuclear Molybdenum Complex with Oxalate Ligand, (enH_2){NH_4[Co(en)_3][Mo_2O_7(C_2O_4)] }_2·2H_2O

The title complex (enH2){NH4[Co(en)3][Mo2O7(C2O4)]}22H2O (C18H70Co2Mo4- N16O24, Mr = 1396.52) was obtained under hydrothermal conditions and its crystal structure has been determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a = 17.8023(8), b = 7.7527(4), c = 16.9781(4) ? b = 103.878(7), V = 2274.8(2) 3, Dc = 2.039 g/cm3, Z = 2, m(MoKa) = 1.878 mm-1 and F(000) = 1408. The final R = 0.0410 and wR = 0.1070 for 4065 observed reflections with I≥2s(I). The crystal structure is composed of bi- nuclear [Mo2O7(C2O4)]4- anions, complex [Co(en)3]2+ cations, protonated ethylenediamine cations, ammonium cations and crystal water molecules, which are held together into a three-dimensional network via hydrogen-bonding interactions. The binuclear structure of [Mo2O7(C2O4)]4- consist of one MoO4 and one MoO6 octahedra through sharing a bridging oxygen atom, where the oxalate ligand acts as a bidentate ligand coordinating to the octahedral molybdenum atom though two deprotonated corboxylate groups.

Synthesis, Crystal Structure and Characterization of the Host-guest Type UOF

A new uranium（Ⅵ）-polycarboxylate framework with honeycomb（6,3） nets {[Zn（phen）_2（H_2O）_2][（UO_2）_2（BDC）_3]·2H_2O}n（1, BDC = benzene-1,4-dicarboxylate） was hydrotherrmally synthesized by the reactions of Zn（NO_3）_2·6H_2O with phenanthroine, UO_2（NO_3）_2·6H_2O and benzene-1,4-dicarboxylate. The complex was structurally characterized by FT-IR spectroscopy, powder XRD and X-ray single-crystal diffraction. Crystal data for 1： monoclinic, space group Cc with M_r = 1522.19, a = 14.9385（10）, b = 20.4922（13）, c = 15.9728（10） ？, β = 100.1240（10）°, V = 4813.5（5） ？~3, Z = 4, D_c = 2.100 g？cm^（–3）, μ = 7.293 mm^（–1）, F（000） = 2872, the final R = 0.0224 and w R= 0.0677 for 6522 observed reflections with I 〉 2σ（I）. Hydrogen bonds and π-π stacking interactions contribute to the structural extension and stabilization. Experimental band gap of about 3.57 e V indicates its broad gap semiconductor nature. UV-Vis spectra and solid-state luminescence were discussed in detail. The compound exhibits photocatalytic activities for the degradation of rhodamine B.

Hydrothermal Synthesis,Crystal Structure and Fluorescent Property of a Novel Mo(V) Phosphate [Zn(Mo^v_6P_4O_(31)H_(10))_2(C_4H_(14)N_3)_2]·2C_4H_(13)N_3·8H_2O

A new molybdenum phosphate [Zn（Mo^v6P4O31H10）2（C4H144N3）2].2C4H13N3.8H2O 1 （C4H13N3 = diethylenetriamine） has been synthesized under hydrothermal condition. Single-crystal X-ray diffraction reveals that compound 1 crystallizes in the monoclinic, space group P21/n, a = 13.1679（3）, b = 22.1240（6）, c = 13.6146（3） A, β= 103.4847（7）°, V = 3856.95（16） A^3, C16H90N12O70P8ZnMo12, Mr = 3035.41, Z = 2, Dc = 2.614 g/cm^3, μ = 2.483 mm^-1, F（000） = 2968, S = 1.014, the final R = 0.0196 and wR = 0.0506 for 7486 observed reflections （1 〉 2σ（I））. Compound 1 consists of two identical rings of six edge-sharing MoOt, octahedra interconnected by one ZnO6 octahedron, whereas the PO4 tetrahedra which share their apices with the MoO6, octahedra are only located on one side of each Mo6, ring. The 2-charge of polyanion [Zn（Mo^v6P4O31H10）2]^2- unit is compensated in the crystal by two mono-protonated diethylenetriamines （C4H14N3）^＋. By hydrogen bonding interactions the polyanion of compound 1 is interconnected to form pseudo threedimensional molybdophosphate. Other characterizations by elemental analyses, IR spectrum and fluorescent spectrum are also described.

Hydrothermal Synthesis and Structure of One New Vanadoarsenate [Zn(dien)(Hdien)]_2[As_6V_(15)O_(42)(H_2O)]·4H_2O

One new arsenic-vanadium cluster, [Zn（dien）（Hdien）]2[As6V15O42（H2O）]·4H2O （1, dien = diethylenetriamine）, has been hydrothermally synthesized and characterized by IR, elemental analysis, TGA, magnetic property and single-crystal X-ray diffraction analysis. Crystal data for 1： monoclinic, space group P21/n, a = 13.959（3）, b = 22.428（5）, c = 22.831（5） A^°, β = 90.733（4）°, Z = 4. X-ray crystallographic study showed that compound 1 is constructed from [As6V15O42（H2O）]^6- polyoxoanions linked together by novel [Zn（dien）（Hdien）]^3＋ complex fragments via hydrogen bonds into a three-dimensional network. Variable temperature susceptibility measurement demonstrates the presence of antiferromagnetic interaction between V^IV cations in 1.

[Co(enMe)_3]_2[As_8V_(14)O_(42)(H_2O)]·10H_2O的水热合成、性质和晶体结构

合成了一种新的砷-钒-氧簇合物[Co(enMe)3]2[As8V14O42(H2O)]10H2O(enMe为1,2-丙二胺),用元素分析、IR和TGA-DTA等进行了表征,并用X射线衍射法测定了晶体结构。结果表明,该晶体属单斜晶系,C2/c空间群,晶胞参数a=28.990(7),b=15.540(6),c=22.77(1),b=131.24(4),Mr=2744.68,V=7714(7)3,Z=4,F(000)=5232,m(MoKa)=7.239mm-1,Dc=2.363g/cm3,R=0.069,Rw=0.073。结构测定表明,结构中簇阴离子[As8V14O42(H2O)]4-与配位阳离子[Co(enMe)3]2+之间靠静电作用相结合,同时通过氢键构成无限的三维骨架结构。

[Ni(2,2'-bpy)_3]MoO_4·7.5H_2O的水热合成和晶体结构

合成了一种新的钼-氧化合物[Ni(2,2 -bpy)3]MoO47.5H2O,用元素分析、IR和TGA- DTA等手段进行了表征,并用X射线衍射法测定了晶体结构。结果表明,该化合物属于单斜晶系,C2/c空间群,a = 23.019(5),b = 13.967(3),c = 23.510(5) ,b = 107.28(3),V = 7217(3) 3,Z = 8,Dc = 1.514 g/cm3,F(000) = 3384,Mr = 822.32,m (MoKa) = 0.934 mm-1。结构由直接法解出,全距阵最小二乘法修正,最终偏离因子R = 0.0358,wR = 0.0797。结构测定表明,结构中阴离子MoO42-与配位阳离子[Ni(2,2 -bpy)3]2+之间靠静电作用相结合,同时与H2O通过氢键构成无机阴离子层。

Synthesis and Characterization of a Reduced Molybdenum(V) Phosphate, (H_3dien)_2(H_2dien)_2[NaMo_(12)O_(24)(OH)_6-(H_2PO_4)(HPO_4)_5(PO_4)_2]·nH_2O (n = 10.92)

A new reduced molybdenum（V） phosphate （H3dien）2（H2dien）2[NaMo12O24 （OH）6 （HEPO4）（HPO4）5（PO4）2]·nH2O （n= 10.92, dien = diethylenetriamine） has been synthesized under hydrothermal conditions and characterized by elemental analyses, IR and X-ray diffraction. C16H96.84MO12N12NaO72.92P8 （Mr = 3046.73） crystallizes in the monoclinic system, space group P21/c with a = 13.3575（18）, b = 21.907（3）, c = 15.654（2）A, β= 110.22（2）°, V= 4298.4（10） A^3 Dc = 2.354 g/cm^3, Z = 2,μ（MoKcr） = 1.966 mm^-1, F（000） = 2990.4, the final R = 0.0357 and wR = 0.1086 for 8739 observed reflections with I 〉 2σ（I）. It consists of sandwich-shaped cluster anions [Na{Mo6P4}2]^10- held together into a three-dimensional supramolecular framework through intermolecular hydrogen-bonding contacts. A probe reaction of the oxidation of acetaldehyde with H2O2 showed that this compound has high catalytic activity in the reaction.

含有两个簇阴离子[As_8V_(14)O_(42)(SO_4)]^(6-)的金属-氧簇合物(H_2en)_6[As_8V_(14)O_(42)(SO_4)]_28H_2O的水热合成与晶体结构

合成了一种新的砷-钒-氧簇合物(H2en)6[As8V14O42(SO4)]28H2O(en为乙二胺),用元素分析、IR和TG-DTA等手段进行了表征,并用X射线衍射法测定了晶体结构。结果表明, 该晶体属单斜晶系,P21/c空间群,晶胞参数a = 20.9235(4),b = 11.9382(2),c = 43.5783(6) 牛琤 = 102.13,V = 10642.1(3) ?,Z = 4,Mr = 4678.01,Dc = 2.920 g/cm3,F(000) = 8944,m = 7.437 mm-1,R = 0.0735,wR = 0.1361。结构测定表明,结构中2个簇阴离子{[As8V14O42(SO4)]6-}与有机铵阳离子[H2en]2+之间靠静电作用相结合,同时与H2O通过氢键构成无限的三维骨架结构。

(H_2en)_2[Se_2Mo_5O_(21)]2H_2O的水热合成、晶体结构与光谱研究

在水热条件下, 以SeO2、V2O5、MoO3、K2CO3、en(乙二胺)作为起始原料, 得到了标题化合物(H2en)2[Se2Mo5O21]2H2O, 利用IR、UV、荧光光谱、单晶-X射线衍射等方法对其进行了表征。结构测定表明, 该化合物属于正交晶系, 空间群: P212121, 化学式: C4H24- Mo5N4O23Se2, 晶胞参数: a = 12.1386(7), b = 17.7118(8), c =11.7092(5) ? V = 2517.4(2) ?, Z = 4, Dc = 2.987 g/cm3, Mr = 1133.89, m = 5.419 mm-1, F(000) = 2144, 最终结构偏离因子R = 0.0285, wR = 0.0400, S = 0.904。该化合物由2个双质子化的en、2个H2O分子以及杂多阴离子[Se2Mo5O21]4-组成。其中,杂多阴离子由5个畸变的MoO6八面体以共边或共顶点形式连接构成一个平面骨架; 2个畸变的SeO3四面体和MoO6八面体以共顶点形式连接, 且位于平面的两侧;质子化的en位于4个[Se2Mo5O21]4-离子围成的四面体空位中, 与杂多阴离子和水分子通过氢键连接成无限三维结构。最后我们用B3LYP方法研究了阴离子簇的电子结构。

萘氧乙酸构筑的铕(Ⅲ)和钐(Ⅲ)配合物的水热合成、晶体结构及荧光性质

用水热方法合成了2个异质同晶镧系稀土配位聚合物,{[Ln2(2-naph)4(H2O)2](2-naph)2·2H2O}n(Eu,1;Sm,2)(2-naph=2-萘氧乙酸根),并通过X-射线衍射的方法测定了它们的结构。2个配合物均为沿着b轴方向扩展的一维链结构,是由一对2-萘氧乙酸配体连接二聚体单元[Ln2(2-naph)4(H2O)2]而形成的。在每个[Ln2(2-naph)4(H2O)2]二聚体单元中,2个螯合-桥连配位模式的2-萘氧乙酸配体和2个桥连配位模式的2-萘氧乙酸配体连接2个Ln(Ⅲ)原子形成了1个次级构筑单元(SBU)。每个Ln(Ⅲ)原子与1个水分子和6个2-萘氧乙酸配体进行连接,形成了1个八配位的变形的四方反棱柱的配位环境。另外,2个桥连配位的2-naph连接2个相邻的Ln(Ⅲ)原子形成了1个8-原子环。单链通过O-H…O氢键连接形成了二维层状超分子结构。此外,配合物1和2的热重分析以及室温下的固态荧光性质也在文中得到进一步研究和讨论。

夹心型钼磷酸盐的水热合成与晶体结构

采用水热法合成了首例含过渡金属铬的夹心型钼磷酸盐〔Ｈ３Ｎ（ＣＨ２）６ＮＨ３〕２Ｈ３｛Ｃｒ〔Ｍｏ６Ｏ１５（ＨＰＯ４）（Ｈ２ＰＯ４）３〕２｝·４Ｈ２Ｏ超分子化合物，用单晶Ｘ－射线测定其晶体结构，该晶体属三斜晶系，空间群Ｐ１。晶胞参数ａ＝１２．１５６（２），ｂ＝１２．８０９（３），ｃ＝１３．５３０（３），α＝１０２．４６（３）°，β＝９３．６７（３）°，γ＝９３．４６（３）°．Ｖ＝２０４６．９（７）３，Ｚ＝１，Ｍｒ＝２７６８．６９，Ｄｃ＝２．２４６ｇ／ｃｍ３，Ｆ（０００）＝１３３７，μ＝２．１６２ｍｍ－１，全矩阵最小二乘法修正至Ｒ＝０．０６６６，ｗＲ＝０．１７４５，独立可观测点数为７１４２。化合物是分别由质子化的１，６－己二胺、水和｛Ｃｒ〔Ｍｏ６Ｏ１５（ＨＰＯ４）（Ｈ２ＰＯ４）３〕２｝７－阴离子构成。

[C_(10)N_2H_(10)]_2[H_2P_2Mo_5O_(23)]·2H_2O的合成、结构及电化学性质

水热法合成一种新化合物[C10N2H10]2[H2P2Mo5O23].2H2O,并通过红外光谱、元素分析、X线单晶衍射分析和电化学分析等手段进行表征.晶体数据结果表明,晶体属于三斜晶系,P-1空间群,晶胞参数分别为a=0.995 15(11)nm,b=1.123 67(13)nm,c=1.758 1(2)nm,α=73.454(1)°,β=84.036(1)°,γ=68.002(1)°,V=1.747 3(3)nm3;Z=2;最后的一致性因子R1=0.030 5,wR2=0.077 3.标题化合物由两个质子化的4,4′-联吡啶和一个杂多阴离子[H2P2Mo5O23]4-组成.循环伏安法显示该化合物具有可逆的氧化还原性能,电子转移数为1,相关电对为Mo(Ⅵ)/Mo(Ⅴ).

h-MoO_3·1/3H_2O的水热合成、晶体结构、红外光谱及Raman振动光谱的研究

采用水热法制备了h-MoO3·1/3H2O(化合物(1)),通过单晶X射线衍射对h-MoO3·1/3H2O的结构进行了进一步的确定,分析表明化合物h-MoO3·1/3H2O的结构基于由MoO6八面体形成的双链,通过共价键的结合形成了具有三维层状结构的多孔化合物,在化合物中含有由12元环和3元环堆积而成的两种隧道,其中水分子占据了12元环隧道.另外,作者研究了化合物(1)的红外光谱和拉曼光谱性质,并与其它相的化合物进行了对比.