Hydrothermal Synthesis,Crystal Structure and Magnetic Properties of a Cobalt(II) Coordination Polymer Assembled by 4-Sulfophthalate and 4,4'-Bipyridine

A novel metal-organic coordination polymer {[Co2（4-sphth）2（4,4＇-bpyh（H2O）4]- [Co（4,4＇-bpy）2（H2O）4]}, （4-sphth = 4-sulfophthalic acid, 4,4＇-bpy = 4,4＇-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and magnetic susceptibility measurements. The complex crystallizes in monoclinic, space group C2/c with a = 18.893（6）, b = 23.080（7）, c = 22.473（7） A, fl = 107.311 （4）°, V = 9356（5） A^3, C76H70Co3N12O22S2, Mr = 1744.35, De = 1.238 g/cm^3,μ（MoKα） = 0.640 mm^-1, F（000） = 3596, Z = 4, the final R = 0.0444 and wR = 0.0846 for 9178 observed reflections （I 〉 2σ（I））. It exhibits a novel three-dimensional supramolecular network formed by hydrogen-bonding and π-π interactions. Variable-temperature magnetic measure shows an overall anti-ferromagnetic behavior for compound 1.

Hydrothermal Synthesis, Crystal Structure and Magnetic Properties of a Novel Zero-dimensional Manganese(Ⅱ) Complex with 2,2′-Diphenic Acid and 1,10-Phenanthroline Ligands

A novel metal-organic coordination polymer [Mn3（2,2′-dipha）3（phen）6]n·3nH2O （2,2′-dipha = 2,2′-diphenic acid, phen = 1,10-phenanthroline） 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and magnetic susceptibility measurements. The crystal crystallizes in triclinic, space group P1 with a = 16.921（5）, b = 18.307（5）, c = 18.450（5）A , α = 113.369（5）, β = 108.529（5）, γ = 102.984（5）°, V = 4553（2）A^ 3, C114H72Mn3N12O14.25, Mr = 2002.66, Dc = 1.461 g/cm^3, μ（MoKα） = 0.488 mm^-1, the final F（000） = 2058, Z = 2, R = 0.0491 and wR = 0.0980 for 9087 observed reflections （I 〉 2σ（I））. In the crystal structure, the manganese atom is six-coordinated with two carboxylate oxygen atoms from different carboxylate groups of the same dipha and four nitrogen atoms from two different phen ligands, showing a slightly distorted octahedral geometry. Fur- thermore, it exhibits a zero-dimensional structure with dipha-Mn-phen- as building units. Variable- temperature magnetic measure shows an overall anti-ferromagnetic behavior for compound 1.

Direct hydrothermal synthesis and magnetic property of titanate nanotubes doped magnetic metal ions

Pure titanate nanotubes and titanate nanotubes doped with Fe^3＋/Ni^2＋/Mn^2＋ ions were synthesized by the hydrothermal method. In this process,titanate nanotubes were first prepared synchronously with doping Fe^3＋/Ni^2＋/Mn^2＋ ions. The morphology,structure,thermal stability and magnetic property of titanate nanotubes were characterized by X-ray diffraction （XRD）,transmission electron microscope （TEM）,and magnetic measurement. The titanate nanotubes transformed into the anatase titania nanocrystals,and further the mixture of anatase and rutile titania along with increasing temperature. The results indicate that the titanate nanotubes doped with Fe^3＋/Ni^2＋/Mn^2＋ ions are paramagnetic behaviors.

Syntheses,Crystal Structures,and Magnetic Properties of Cobalt(Ⅱ) Complexes with 1,1-Cyclohexanediacetic Acid

Two new Co（Ⅱ） coordination polymers,{[Co_3（Hchda）_2（chda）_2（bpp）_2（H_2O）_2]}_n 1 and {[Co（chda）（bpe）（H_2O）]·3H_2O}_n 2（H_2chda = 1,1-cyclohexanediacetic acid,bpp = 1,3-bis（4-pyridinyl）propane and bpe = 1,2-bis（4-pyridinyl）ethylene）,were hydrothermally synthesized and then characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis（TGA）,and single-crystal X-ray diffraction.Complex 1 possesses an infinite metal-organic layer based on triply bridged linear trinuclear subunits and complex 2 exhibits a square（4,4） grid layer with dangling lateral arms resulting from eight-membered rings above and below the layer.In addition,magnetic properties of complexes 1 and 2 are also given.

A New 3-D Supramolecular Framework Built by Co4-Substituted Sandwiched Phosphotungstates, Organoamines and Co-Complexes: Synthesis, Structure, and Property

A neoteric organic-inorganic hybrid Co-substituted phosphotungstate H6{[Co(en)2(OAc)2]2[Co4(H2 O)2(PW9 O34)2]}·2 H2 en·36 H2 O(1, en = enthylenediamine) has been made under hydrothermal conditions and characterized by IR spectrum, thermogravimetric analysis, diffuse-reflectance spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction and cyclic voltammetry, respectively. Crystal data for 1: monoclinic, P21/c, a = 18.2234(12), b = 15.3696(9), c = 20.1706(17) A, β = 106.563(8)°, V = 5415.1(7) A3, Z = 2, Mr = 6072.30, Dc = 3.724 g/cm3, μ = 20.087 mm-1, F(000) = 5540, R = 0.0585, w R = 0.1543 and S = 1.024. Single-crystal X-ray structure analysis reveals that compound 1 exhibits a 3-D supramolecular framework via H-bonding interactions, in which the discrete Co-complex is modified by two types of organic ligands, en and acetate. In addition, the adsorption experiments demonstrate compound 1 possesses a remarkable capability for scavenging of methylene blue.

Synthesis,Structure and Electrochemical Property of a Supramolecular Compound(H_2en)_2[Cu(en)_2(H_3O)_2][Mo_8O_(28)]

A supramolecular compound（H2en）2[Cu（en）2（H3O）2][Mo8O28]（en=ethylenediamine） was hydrothermally prepared and confirmed by elemental analysis and TG analysis.Single-crystal X-ray analysis reveals that the crystal crystallizes in the triclinic system,space group P1 with a=9.4635（4）,b=9.8645（5）,c=10.9794（5）A,α=69.2050（10）,β=72.3730（10）,γ=78.4510（10）o,Mr=1559.55,V=908.24（7）A^3,Z=1,Dc=2.851 g/m^3,F（000）=749,μ=3.350 mm^-1,S=1.000,the final R=0.0217 and wR=0.0567.The compound consists of（H2en）^2＋,[Mo8O28]^8-anion and [Cu（en）2（H3O）2]^2＋ cations and constructs a 3D supramolecular structure through hydrogen bonds between the nitrogen atoms from en of [Cu（en）2（H3O）2]^4＋ fragments and the terminal oxygen atoms from the [Mo8O28]^8-polyoxoanions.The electrochemical behavior of this compound has been studied in detail based on a solid bulk modified carbon paste electrode of compound（CPE）.

Hydrothermal synthesis, crystal structure and magnetic properties of a Dy~Ⅲ-Fe~Ⅲ heteronuclear complex

A new 3d-4f heteronuclear complex [Fe（phen）3]2[FeDy（H2O）（tiron）3]·6H2O （1,Na2H2tiron=disodium 4,5-dihydro-xybenzene-1,3disulfonate） was synthesized by the hydrothermal reaction. The complex crystallized in the cubic system, space group P213 with the cell parameters：a=2.18786（14）nm, V=10.4727（12）nm3 , Z=4, F（000）=4720, R1=0.0493, wR2 =0.1165, S=1.05. In each [FeDy（H2O）（tiron）3]6-unit, it was revealed that the Fe3＋ ion was in a FeO6 distorted trigonal anti-prism coordination polyhedron completed by six phenolate O atoms from three tiron 4- ligands, while Dy3＋ in a DyO7 distorted monocapped trigonal anti-prism coordination polyhedron completed by three phenolate μ2-O atoms and three O atoms from sulfonate groups of three ligands and one O atom from water. The magnetic properties of the complex was determined in the range of 2-300K, indicating the antiferromagnetic interaction between the central DyIII-FeIII ions.

Hydrothermal Synthesis and Magnetic Properties of SmCr0.5M0.5O3（M=Fe and Mn） Micro-plates

Nanostructured B-site Fe and Mn doped SmCrO3 was prepared by mild hydrothermal growth. The as-prepared crystals are mainly micrometer-scale plates, ranging from rhombus（SmCr0.5Fe0.5O3） to elongated hexagonal（SmCr0.5Mn0.5O3）, and finally to well-edged rectangular（SmCr0.17Mn0.5Fe0.33O3） plates. Fe and Mn doped SmCrO3 crystals are indexed into Pbnm space group. The cell parameters of SmCr0.5Fe0.5O3 are slightly smaller than that of pristine SmCrO3. Binding energy analysis of Cr, Mn and Fe in SmCr0.17TMn0.5Fe0.33O3 sample indicates that they all possess ＋3 oxidation states. Temperature dependent magnetization of the as-prepared samples presents obviously stronger ferromagnetic interactions than the undoped counterparts. This work represents a remarkable development for hydrothelmal synthesis into fabricating perovskite oxide crystals with uniform distribution of doping ions.

Hydrothermal Synthesis, Crystal Structure and Properties of a New Copper Coordination Polymer [Cu2I（C7H5N4）2]n with 3-（Pyridin-2-yl）-1,2,4-triazole) Ligand

A new copper coordination polymer[Cu2I(C7H5N4)2]n(1)with the 3-(pyridin-2-yl)-1,2,4-triazole(Hpt)and copper iodide was synthesized.It crystallizes in the triclinic space group P1 with a=8.6380(9),b=9.2434(9),c=11.8588(12)A,α=99.5890(10)o,β=109.0990(10)o,γ=105.2800(10)o,V=829.25(15)A^3,Dc=2.180 g/cm3,Z=2,F(000)=522,GOOF=1.046,the final R=0.0245 and wR=0.0598.The crystal structure shows that two copper ions are bridged by twoμ2-η1:η0-3-(pyridin-2-yl)-1,2,4-triazole anions and two iodide ions.The coordination environments of the Cu ion are Cu(1)N5 and Cu(2)N2I2,giving distorted square pyramidal geometry and trigon pyramid geometry.The magnetic and fluorescent properties of 1 were studied.

Hydrothermal Syntheses, Supramolecular Structures and the Third-order Non-linear Optical Properties of Three Copper(I) Halide Amine Complexes Connected via Secondary Bonding Interactions

The hydrothermal reactions of CuI, KI and bidentate amines [ 1,10 phenanthroline (phen) or ethylenediamine (en)] gave the three copper(I) halide compounds, Cu3I3(phen)2 (1), CuI(phen)2 (2) and 2 (3), which were structurally characterized via singlecrystal Xray diffraction studies. Hydrogen bonds and ππ interactions are the most remarkable structural features of the title compounds. All can be described as higherdimensional supramolecular compounds connected via these secondary bondings. Moreover, the title compounds were characterized by elemental analyses, IR spectra and TGA analyses. The thirdorder nonlinear optical properties of the title compounds were also investigated and all exhibit nicer nonlinear absorption and selffocusing performance.Keywords copper(I) halide, hydrothermal synthesis, the thirdorder nonlinear optical property, supramolecular structure

Synthesis, Structure, Thermal and Magnetic Properties of a New Open-framework Borophosphate： NH4Mn（H2O）2BP2O8·H2O

Using new template agent, a new borophosphate compound, NH4Mn（H2O）2BP2O8·H2O was hydrothermally prepared and structurally characterized. It crystallizes in a hexagonal space group P6 1 22 with lattice parameters a= 0.9652（2） nm, c= 1.5792（5） nm, V= 1.2740（5） nm^3 and Z=6. The structure has a three-dimensional open-frame work with borophosphate helical ribbons ^1∞{ [BP2O8 ]^3-} and MnO4（H2O）2 octahedra. The water molecules are positioned inside the helical channels. Very interestingly, the ammonium ions are located outside the loop of the free helical ribbons via the strong hydrogen bonds, which is different from the borophosphate analogue reported. The magnetization of the title compound is paramagnetic down to 5 K of the Curie-Weiss type within the measured range of 5=-00 K with θ=-7.3 K, indicative of very weak antiferromagnetic interactions. The thermal decomposition of the compound was also described.

Mixed-ligands Self-assembly Strategy Affording a New 4-Fold Interpenetrated 3D Co(Ⅱ)-based Coordination Polymer: Synthesis, Crystal Structure and Magnetic Property

A new Co(Ⅱ)-based coordination polymer, namely [Co(L)0.5(4,4?-bipy)0.5(H2 O)2]n(1,H4 L = 1,3-di(3?,5?-dicarboxylphenyl)benzene, 4,4′-bipy = 4,4′-bipyridine), has been hydrothermally synthesized using the mixed-ligands self-assembly strategy and further fully characterized. The crystal structure is of monoclinic, space group C2/c with a = 18.9124(10), b = 11.6150(5), c =15.4380(6)A,β= 110.989(5)°, V = 3166.2(2)A^3, C16 H13 CoNO6, Mr = 374.20, Z = 8, Dc = 1.570 g·cm^–3, F(000)= 1496,μ= 1.116 mm^–1, R = 0.0461 and wR = 0.1312 for 2328 observed reflections(I > 2s(I)). The crystal structure analysis revealed that 1 is a 4-fold interpenetrated three-dimensional(3D) framework with(3,4)-connected dmd-type topology. Moreover, the thermal stability and magnetic property of 1 were also investigated.

Hydrothermal Synthesis and Characterization of PEG-Mn_3O_4 Nanocomposite

Here, we report on the synthesis of PEG-Mn_3O_4 nanocomposite(NP's) via a hydrothermal route by using Mn(acac)2, ethanol, NH3 and PEG-400. The crystalline phase was identified as Mn_3O_4. The crystallite size of the PEG-Mn_3O_4 nanocomposite was calculated as 12±5 nm from X-ray line profile fitting and the average particle size from TEM was obtained as 200 nm. This reveals polycrystalline character of Mn_3O_4 NP's. The interaction between PEG-400 and the Mn_3O_4 NP's was investigated by FTIR. Temperature independent AC conductivity of PEG-Mn_3O_4 nanocomposite beyond 20 k Hz provides a strong evidence of ionic conduction through the structure. The conductivity and permittivity measurements strongly depend on the secondary thermal transition of nanocomposite beyond 100. Above that temperature, Mn_3O_4 particles may interact with each other yielding a percolated path that will facilitate the conduction. On the other hand, the relatively lower activation energy(Ea=0.172 e V) for relaxation process suggests that polymer segmental motions of PEG and electrons hopping between Mn2+and Mn3+may be coupled in the sample below 100. Room temperature magnetization curve of the sample does not reach to a saturation, which indicates the superparamagnetic character of the particles. As the temperature increases, the frequency at which(ε′′) reaches a maximum shifted towards higher frequencies. The maximum peak was observed at 1.4 k Hz for 20 while the maximum was detected at 23.2 k Hz for 90.

Large-scale synthesis of nickel sulfide micro/nanorods via a hydrothermal process

Rhombohedral-phase NiS micro/nanorods were synthesized on a large scale through a hydrothermal method using NiCl2·6H2O and thiourea crystals as starting precursors. Recrystallized thiourea was observed to play an important role in the formation of mi- cro/nanosized rods and flower-like structures. The molar ratio and reaction temperature of the precursors influenced the morphology and phase of NiS products. Pure rhombohedral NiS micro/nanorods were obtained on a large scale when the molar ratio between NiCl2·6H2O and thiourea crystals was fixed at 2：1, and the mixture was heated at 250℃ for 5 h. Flower-like NiS nanostructures were formed when the molar ratio between NiCl2·6H2O and thiourea crystals was maintained at 1：1. The Raman and Fourier-transform infrared （FTIR） spectra of the as-prepared rhombohedral NiS micro/nanorods were collected, and their magnetic properties were investigated. The results showed that the FTIR absorption peaks of the as-prepared product are located at 634 cm^-1 and their Raman peaks are located at 216 and 289 cm^-1; the as-prepared NiS micro/nanorods exhibited weak ferromagnetic behavior due to the size effect.

AgCu(IO3)3：Synthesis,Crystal Structure and Magnetic Property

A new mixed metal iodate, namely Ag Cu（IO3）3, has been prepared using hydrothermal method. Ag Cu（IO3）3 crystallizes in the triclinic group P1 with a = 7.3063（6）, b = 7.8050（6）, c = 8.2447（6） A, α = 67.212（7）, β = 74.978（7）, γ = 80.972（7）°, V = 417.80（6） A^3 and Z = 2. The structure features one-dimensional [Cu（IO3）3]n^n- anionic chains that are separated by Ag~＋ cations. Such [Cu（IO3）3]n^n- chain is composed of [Cu2O（11）]n chain decorated by unidentate hanging and bidentate bridging iodate groups. Thermal study implies that Ag Cu（IO3）3 is thermally stable up to 460 oC and the optical measurement determined the optical band gap of 3.11 eV with a broad absorption band centered at 765 nm. Magnetic investigations show that Ag Cu（IO3）3 is a soft ferromagnet.

Synthesis, Crystal Structure and Luminescent Property of [Zn(C_(12)H_9O_3)_2(C_(10)H_8N_2)]_n·nH_2O

Under hydrothermal condition, the reaction of 2-naphthoxyacetic acid with ZnCl2 and 4,4′-bipyridine （4,4′-bipy） has afforded a new Zn（Ⅱ） compound, [Zn（C12H9O3）2（C10H8N2）]n·nH2O1, which was structurally characterized by single-crystal X-ray diffraction analysis. The crystal is of monoclinic, space group P21/c with a = 7.7335（2）, b = 19.3834（4）, c = 20.1707（4） A, β = 104.9830（10）°, V = 2920.82（11） A^3, C34H28ZnN2O7, Mr = 641.95, Z = 4, Dc = 1.460 g/cm^3,μ = 0.895 mm^-1, F（000） = 1328, R = 0.0406 and wR = 0.0876 for 4417 observed reflections （I〉 2σ（I）） Complex 1 consists of one-dimensional zigzag chains deriving from Zn（C12H9O3）2 units linked by 4,4′-bipy ligands, and lattice water molecules decorate between the chains. Non-covalent interactions, such as hydrogen-bonding and aromatic π-π interactions, lead to the formation of a 3D network structure. The thermogravimetric analysis （TGA） and luminescent property for 1 have also been studied in this paper.

Syntheses,Crystal Structures and Properties of Co(Ⅱ) and Cu(Ⅱ) Complexes with 5-Nitro-1,2,3-benzenetricarboxylic Acid

Two new coordination polymers,{[Co（O2N-Hbtb）（phen）（H2O）3]·2H2O}n 1 and {[Cu3（O2N-btb）2（bipy）2（H2O）4]·4H2O}n 2（O2N-H3btb=5-nitro-1,2,3-benzenetricarboxylic acid,phen=1,10-phenanthroline,bipy=2,2＇-bipyridine）,were prepared through hydrothermal reactions of Co（Ⅱ） or Cu（Ⅱ） salt with O2N-H3btb in the presence of different auxiliary N-donor ligands.Their crystal structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis and IR spectroscopy.In the two complexes,O2N-H3btb ligand acts as monodentate and bis-monodentate modes,respectively.Complex 1 displays a two-dimensional layered structure through the inter-and intramolecular hydrogen bonding interactions while complex 2 has an O2N-btb bridged one-dimensional chain which is extended into a three-dimensional network by hydrogen bonding interactions.The magnetic properties of complex 2 are investigated over the temperature range of 2～300 K and ferromagnetic interactions are observed.

A 2D Cobalt(Ⅱ) Coordination Polymer [Co(iqnc)_2]_n: Synthesis, Crystal Structure and Characterization

A new cobalt（Ⅱ） coordination polymer with the formula of [Co（iqnc）2]n（1, iqnc = l-isoquinolinecarboxylate） has been synthesized through hydrothermal synthesis and structurally characterized by single-crystal X-ray diffraction method. The title coordination polymer represents a two-dimensional layer structure featuring adjacent one-dimensional [Co（iqnc）2]n chains connected with each other by uncoordinated oxygen atoms of carboxylate. Crystal data： monoclinic, space group P21/c, a = 15.4302（2）, b = 5.6743（7）, c = 9.2307（1） A, β = 98.459（2）o, V = 799.41（2） A3, Z = 2, S = 1.019, the final R = 0.0346, w R = 0.0876（I 2σ（I）） and R = 0.0477 and wR = 0.1159 for all reflections. In addition, elemental analysis, IR, and magnetism properties are presented.

水热法制备纳米镍锌铁氧体粉体及其磁性能

用水热法分别在200℃和220℃下反应5h制备了纳米级镍锌铁氧体(Ni0.5Zn0.5Fe2O4)粉体。用X射线衍射(X-ray diffraction,XRD)分析合成的纳米Ni0.5Zn0.5Fe2O4的物相,结果表明:200℃水热反应5h得到的纳米Ni0.5Zn0.5Fe2O4粉体中含有γ-Fe2O3,220℃水热反应5h可以得到纯纳米Ni0.5Zn0.5Fe2O4粉体。用透射电镜(transmission electronmicroscope,TEM)、Mssbauer谱(Mssbauer spectroscopy,MS)、Fourier红外分析(Fourier transform infrared spectroscopy,FTIR)、振动样品磁强计(vibrating sample magnetometer,VSM)等方法表征纯纳米Ni0.5Zn0.5Fe2O4粉体。TEM结果表明:纳米Ni0.5Zn0.5Fe2O4粉体粒子为球形,粒径约为20nm。室温MS结果表明:大部分纳米Ni0.5Zn0.5Fe2O4粉体粒子表现出铁磁性,少量的表现出超顺磁性。FTIR分析表明:样品在577cm-1和420cm-1处出现NiZn铁氧体的特征峰。磁滞回线结果表明:纳米Ni0.5Zn0.5Fe2O4粉体粒子的饱和磁化强度为38.14A?m2/kg,剩磁为17.32A?m2/kg,矫顽力为29275.29A/m。

钴、镍-氨基三乙酸配位聚合物Na[M(nta)]·H_2O(M=Co,Ni)的水热合成、结构与磁性

Two new three-dimensional coordination polymers, Na [M(nta)]·H 2O(M=Co, Ni) were hydrothermally synthesized and their structures were solved by single-crystal X-ray diffraction. Their structures were analogous and the two crystals belong to the orthorhombic system with space group P2 1, and cell parameters a=0.785 7(9) nm, b=0.974 3(12) nm, c= 1.219 0(18) nm, V=0.933 4(2) nm 3, Z=4 for Na [Co(nta)]·H 2O and a=0.796 7(16) nm, b= 0.975 2(2) nm, c=1.218 2(2) nm, V=0\^946 5(3) nm 3, Z=4 for Na [Ni(nta)]·H 2O. The structures of the title compounds are considered to be four M(nta) - octahedra connected by the sodium atoms, thus the three-dimensional tunnels were formed. Variable temperature magnetic susceptibility indicates that the antiferromagnetic interaction exists in Na[Co(nta)]·H 2O and Na [Ni(nta)]·H 2O.