A new 3-D Gd–Cu heterometallic polymer [Gd_2Cu_3(bpy)_2-(ip)_6]·6H_2O with a non-interpenetrated α-Po net

A new 3-D porous Gd-Cu heterometallic polymer [Gd2Cu3(bpy)2(ip)6]·6H2O (1) (bpy = 2,2'-bipyridine, H2ip = isophthalic acid) has been hydrothermally synthesized and structurally characterized. Compound 1 crystallizes in the triclinic space group P1and displays a 3-D non-interpenetrated α-Po network with 1-D channels filled transversely by the hexa-nuclear chain-like (H2O)6. The EPR and thermal stability of 1 were investigated.     

Hydrothermal synthesis and crystal structure of copper （Ⅱ） coordination polymer composed of helix-like chains： [Cu（NIeH）（bpy）]

Hydrothermal reactions of Cu （Ⅱ） acetate, 2,2＇-bipyridyl （bpy） with 5-nitroisophthalic acid （H2NIPH） resulted in a new coordination polymer [Cu（NIPH）（bpy）] 1. Single crystal X-ray diffraction experiment indicates that 1 possesses a single helixlike chains, of which Cu atoms are coordinated by NIPH ligands and bpy ligands. Compound 1 crystallizes in the space group P2（ 1）/c, a = 0.955（19） nm, b = 1.259（3） nm, c = 1.3737（3） nm, ,6= 95.13（3）°, V= 1.6455（6） nm^3 and Z = 4. The TGA analysis shows that 1 has no remarkable weight loss up to 284℃, as a result of its high thermal stability. Magnetic measurements indicate an antiferromagnetic behavior of compound 1.     

Synthesis and structure of 3D heterometallic （3d-4f） coordination polymers： {[Ln2Cu（pydc）4（H2O）6]·2H2O}n

Two new 3D heterometallic （3d-4f） coordination polymers {[Ln2Cu（pydc）4（H2O）6]·2H2O}n [Ln = Eu （1） and Gd （2）] have been synthesized by hydrothermal reactions and characterized by elemental analysis, X-ray single-crystal analyses, and IR spectroscopy. X-ray crystal structure analyses show that 1 and 2 possess 3D networks and strong intramolecular hydrogen bonding interactions which was confirmed by thermogravimetric （TG） analysis.     

Lithium bond structures of HnY （n=2, 3; Y=O,S, N）…LiNH2 and the abnormal blue shift of N-Li bond

The optimized geometries of the complexes between HnY （n=2, 3; Y=O, S, N） and LiNH2 have been calculated at the B3LYP/6-311＋＋G^＊＊ and MP2/6-311＋＋G^＊＊ levels. Three stable complexes were obtained. Frequency analysis showed that the enlarged 2N-4Li presents the abnormal blue shift in three complexes. The calculated binding energy with basis set super-position error （BSSE） and zero-point vibrational energy （ZPE） corrections of complex Ⅰ-Ⅲ is -58.65, -31.66 and -69.59 kJ·mol^-1 （MP2）, respectively. Natural bond orbital theory （NBO） analysis has been performed, and the results revealed that the H2O…LiNH2 （complex I） and H3N…LiNH2 （complex Ⅲ） are formed with coexisting σ-s and n-s type lithium bond interactions, complex Ⅱ is formed with ττ-s type lithium bond interaction between HnY （n=2,3; Y=O, N） and LiNH2, and H2S…LiNH2 （complex Ⅱ） is formed with n-s type lithium bond interaction between H2S and LiNH2. Natural resonance theory （NRT） and atom in molecule （AIM） theory have also been studied to investigate the bond order and topological properties of the lithium bond structures.     

The influence of molar ratios of Ce/Zr on the selective catalytic reduction of NOx with NH3 over Fe2O3-WO3/CexZrl-xO2 （0 〈 x 〈 1） monolith catalyst

A series of CexZrl_xO2 （0 ≤ x ≤ 1） with dif- ferent molar ratios of Ce/Zr were syhthesized via coprecip- itation method, and Fe2O3-WO3/CexZrl-xO2 monolithic catalysts were prepared, for selective catalytic reduction of nitrogen oxides by ammonia （NH3-SCR）. The structural properties and redox behavior of the catalysts were com- prehensively characterized by N2 physisorption, X-ray diffraction （XRD）, X-ray photoelectron spectra （XPS）, H2-temperature programmed reduction （H2-TPR） and activity measurement for NH3-SCR. The results showed that the NH3-SCR activities of the catalysts were gradually enhanced by increasing the molar ratios of Ce/Zr, especially the low- temperature catalytic activity and the reaction temperature window. Fe2O3-WO3/Ceo.68Zro.3202 monolithic catalyst presented the best NH3-SCR activity among the investigated catalysts, more than 90 % NOx could be removed in the temperature range of 247-454 ℃ on the catalyst under the gas hourly space velocities of 30,000 h- 1. And it always held more than 99 % N2 selectivity and less than 20 ppm （1 ppm =10-6 L/L ） N20 generation concentration between 200 and 500 ℃, the catalyst also displayed its strong resistance of H20 and SO2. Good textural and structural properties, more surface Fe, Ce and active oxygen were together contributed to the excellent NH3-SCR performance of Fe2O3-WO3/ Ce0.68Zr0.32O2 catalyst.     

（NH_3CH_2CH_2NH_3）_4[CuV_6O_8（HPO_4）_6（PO_4）_2（H_2O）_2]·4 H_2O的水热合成及晶体结构

利用中温水热技术合成了新型层状磷钒铜多金属氧酸盐（NH3CH2CH2NH3）4[CuV6O8（HPO4）6（PO4）2（H2O）2].4 H2O,采用元素分析、红外光谱、热重分析和X射线单晶结构分析对其进行了表征.结果表明：该化合物属于单斜晶系,C2/c空间群;晶胞参数a=2.0760 nm,b=1.0030 nm,c=2.3784 nm,α=90°,β=101.17°,γ=90°,V=4.8586 nm3,Z=8,R1=0.0719,wR2=0.1432.     

Three new zinc（Ⅱ） coordination polymers： Modulation of extended structures driven by assistant ligands

Three new complexes, [Zn（dtb）（4,4′-bipy）]·5H2O （1）, [Zn（dtb）（bpp）]·H2O （2） and [Zn（dtb）（phen）2]·CH3- CH2OH·H2O （3） （dtb = 5,5′-dithiobis（2-nitrobenzoic acid）, 4,4′-bipy = 4,4′-bipyridine, bpp = 1,3-bi（4-pyridyl） propane, phen = 1,10-phenanthroline）, have been constructed by dtb ligand and zinc salt in the presence of different assistant N-containing ligands under hydrothermal conditions. The structures of the complexes were established by single-crystal X-ray diffraction analysis. Although compounds 1 and 2 are both 2D networks, the cavities＇ forms and pitch of helix are different. The structure of compound 3 shows a 1D helical chain, and is extended by the supermolecule interactions into a 2D framework. These neutral polymeric complexes exhibit structural and dimensional diversity due to the different coordination modes of the flexible dtb ligand and the effect of assistant ligands.     

Hydrothermal synthesis,structures and properties of metal phosphonates based on m-xylylenediphosphonic acid

In this work, a series of new metal phosphonates were hydrothermally synthesized and structurally characterized based on m-xylylenediphosphonic acids （H4L）, including [M（H2L）（bpy）] （M = Mn 1, Co 2）, [MH2L）（phen）] （M = Co 3, Cu 4）, and [Cu2（H2L）2（bpy＂）2] 5 （bpy = 2,2＇-bipyfidine, phen = 1,10-phenanthroline, bpy＂ = 4,4＇-dimethyl-2,2＇- bipyridine）. X-ray diffraction indicated that compounds 1 and 2 were isomorphic. Complexes 3 and 4 were shown to crystallize in different space groups but had similar crystallographic units. In the complexes, H4L was seen to partially deprotonate to afford H2L^2-. The H2L^2- ligands in 1-4 functioned as tetradentate ligands with each phosphonate group adopting bidentate coordination mode with two M centers to generate a 2D layer. In addition, the H2L^2- anions in 5 functioned as tfidentate ligands with one phosphonate group adopting the bidentate mode and another phosphonate group adopting the monodentate mode, thus linking three Cu atoms to provide a 1D chain. The IR and thermal stabilities of these compounds were subsequently examined.     

配合物[Cu（phen）_2（H_2O）]（NO_3）_2的合成及晶体结构

在乙醇水溶液中以4-氯苯氧乙酸、邻菲啉、Cu（NO3）2.3H2O为反应物合成了配合物[Cu（phen）2（H2O）]（NO3）2,并通过元素分析、红外光谱和X射线单晶衍射法进行表征.该晶体属单斜晶系,C2/c空间群,晶胞参数为：a=2.264 2（5）nm,b=0.728 10（15）nm,c=1.661 4（3）nm,β=123.76（3）°,V=2.277 1（8）nm3,Mr=566,Dc=1.648 g/cm3,F（000）=1 152,Z=4,最终偏离因子R1=0.052 6,ωR2=0.143 1.配合物中Cu离子与分属于2个邻菲啉配体的4个N原子以及来自水分子的1个O原子配位.     

Synthesis and properties of a Pr（Ⅲ） complex with 2-acetylbenzimidazoledehyde-glycine Schiff-base ligand

Abstract The 2-acetyl-benzimidazoledehyde-glycine Schiff-base ligand and the corresponding Pr（Ⅲ） complex Pr2L3（NO3）3· 2CH3OH （L=C11H10N3O2） were synthesized in methanol and characterized by a series of methods, including chemical analysis, elemental analysis, TOF-MS, ^1H NMR, UV-, IR-, Raman spectra, thermal analysis, and the three-dimension fluorescence excitation and emission spectra. The Pr（Ⅲ） complex exhibits extraordinary water-solubility and the Pr（Ⅲ） hydroxide appears at pH≥13. The complex also possesses specific fluorescent properties. Thus, at the excitation wavelengths 200.0-280.0 and 260-350 nm the fluorescence bands were observed at 290.0 and 400.0 nm, respectively.     

Synthesis and formation mechanism of micro/nano flower-like MgCO3·5H2O

Micro/nano magnesium carbonate pentahydrate（MgCO3 ·5H2 O） with flower-like morphology was synthesized using magnesite as a substrate and potassium dihydrogen phosphate as an additive. The synthesized samples were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry and differential scanning calorimetry. The influence of pyrolysis time on crystal morphology was explored. The formation mechanism was investigated on the basis of the characterized results and the crystal structure of MgCO3 ·5H2 O. The results showed that the flower-like MgCO3 ·5H2 O was 1.5-3.0 μm in length and 100-500 nm in diameter and was successfully obtained with a pyrolysis time of 30 min. The formation mechanism of flower-like MgCO3 ·5H2 O is suggested to be the selective adsorption of potassium dihydrogen phosphate on the surface. The process of flower-like crystal growth is as follows： amorphous nanoparticles formation, acicular and rod monocrystal formation, flower-like monocrystal formation, and flower-like polymers（MgCO3 ·5H2 O） crystallization. In the MgCO3 ·5H2 O crystal, the magnesium ion presents two different octahedral coordinations corresponding to2 26 Mg（H O）＋and2 2 2 4 23 [Mg（H O）（CO） ]--, and the chemical formula of the crystal is2 2 6 2 4 23 Mg（H O） Mg（H O）（CO）2.     

Eu（bpy）2（NO3）3（H2O）2/Nafion修饰于金电极上的电化学发光性质研究（英文）

本文合成了铕-联吡啶的二元配合物Eu(bpy)2(NO3)3(H2O)2,用元素分析、红外及紫外光谱对配合物进行了表征.采用循环伏安法,研究了用Nafion将Eu(bpy)2(NO3)3(H2O)2修饰于金电极上的电化学发光行为.讨论了介质、pH对该体系电化学发光性质的影响,推测了Eu(bpy)2(NO3)3(H2O)2电化学发光的机理.结果表明:在没有共反应试剂存在的条件下,Eu(bpy)2(NO3)3(H2O)2在pH 8.0的硼砂缓冲溶液中可以产生较强的电化学发光,其发光体可能为Eu*(bpy)2(NO3)3(H2O)2.     

氮杂环卡宾前体[HO-4，6-di-C（CH3）3-C6H2-2-CH2{CH（NCHCHN）CH3}]CI的合成及结构

利用4,6-’Bu2-1-（HO）C6H2CH2CI与甲基咪唑反应成功的合成芳氧功能化的氮杂环卡宾前体[HO-4,6-di-C（CH3）3-C6H2-2-CH2{CH（NCHCHN）CH3}]CI,化合物通过了1HNMR和X-ray衍射表征。晶体结构表明其晶体属单斜晶系,空间群为c2／e,化学式为C19H29CIN2O,晶胞参数为a=32．034（14）A,b=8．630（4）A,c=14．695（7）A,α（deg）=90deg,β（aeg）=106．305（10）deg,γ（aeg）=90deg,V（A3）=3899（3））A3,Z=8,最终R=0.1705,ωR=0．1766。     

[Ca（H—Sulf）（H2O）6]（H—Sulf）·3H2O的合成及晶体结构

Ca（OH）2与柳氮磺胺吡啶（H2-Sulf）反应生成化合物[Ca（H—Sulf）（H2O）6]（H—Sulf）·3H2O。单晶X-射线衍射结构分析表明,标题化合物的化学式为C36H44CaN8O19S2,Mr=996．99,属三斜晶系,P-1空间群,晶胞参数：a=1．15786（11）nm,6—1．50224（15）nm,c=1．53953（15）nm,a=113．129（2）°,β=109．302（2）°,γ=92．477（2）°,V=2．2775（4）nm^3,Z=2,Dc=1．454Mg／m^3,R1=0．142,wR2=0．297（I〉2σ（I））,5=1．027。标题化合物为离子型化合物,中心Ca（Ⅱ）采用七配位的变形加帽八面体几何构型,柳氮磺胺吡啶的羧基采用单齿配位方式与Ca（Ⅱ）形成配位键,羟基和吡啶N均未参与配位。在晶胞堆积中,化合物通过复杂分子内和分子间氢键形成三维的超分子结构。     

Crystal structure and surface photo-electric property of Mn（Ⅱ） coordination supramolecules

Two Mn（Ⅱ） coordination supramolecules, [Mn2（C8HTO2）4（phen）2（p-H20）] （1） and [Mn2（btec）（phen）2（H2O）6]·2H2O （2） （phen=1,10-phenanthroline, H4btec=1,2,4,5-benzenetetracarboxylic acid）, were synthesized by hydrothermal method. The crystal structures of the complexes were determined by X-ray single crystal diffraction. The result indicates that （1） and （2） are both binuclear Mn（Ⅱ） complexes. The existence of hydrogen bonds makes the binuclear complexes become further connected to coordination supramolecules, which possess 1D and 3D infinite structures respectively. The complexes were identified by IR, UV-Vis, surface photovoltage spectrum （SPS） and field-induced surface photovoltage spectrum （FISPS）. The results of SPS for the complexes indicate that they both exhibit positive surface photovoltage response bands in the range of 300-600 nm. The SPS phase spectrum and FISPS of complexes indicate that they show certain p-type semiconductor characteristic. However, the intensity, position and number of the SPV response bands are different obviously. The difference of the SPV response bands is mainly attributed to the different structures of the complexes and the different coordination environment of Mn（ll） in the two complexes. This paper discusses the action of hydrogen bonds in the construction of the supramolecule and the change on the surface photovoltage of complex in different coordination environment.     

配位聚合物Ni（2，6-DPC）2Ni（H20）5·2H20的水热合成与表征

在水溶剂中通过2,6-吡啶二羧酸和NiCl2·6H2O反应生成三维配位聚合物Ni（2，6-DPC）2Ni（H2O）5·2H2O（DPC=2,6吡啶二羧酸）1。对其进行元素分析、红外光谱分析、热重量分析和单晶X射线衍射测定。该配合物属P2（1）/c。晶胞参数a=8．3261（17）A，b=27．227（5）A，c=9．6...     

[V^（Ⅳ） O{salen（3-OMe）}2（CH3OH）]·H2O的合成与晶体结构

1,3-二氨基硫脲双缩邻香草醛,偏钒酸铵,乙二胺,加入吡啶,甲醇和水的混合溶剂合成一种新的[V（Ⅳ）O{salen（3-OMe）}2（CH3OH）].H2O配合物,并进行了红外和晶体结构表征.该晶体属于三斜晶系,P1群.晶胞参数为：a=0.671 50（14）nm,b=0.965 20（19）nm,c=1.600 7（3）nm,α=100.715（3）°,β=101.587（3）°,γ=94.787（3）°,V=0.990 7（3）nm3,Z=2,Dc=1.486 g.cm-3,μ=0.545 mm-1,F（000）=462,R1=0.034 8,ωR2=0.066 6,配合物中钒中心为六配位的扭曲八面体构型.     

Theoretical study on the lithium bond interaction of furan homologues C4H4Y （Y=O,S） with LiCH3 via DFT and MP2

The optimizations geometries and interaction energy corrected by BSSE of the complexes between C4H4Y （Y=O, S） and CHiLi have been calculated at the B3LYP/6-311＋＋G^＊＊ and MP2/6-311＋＋G^＊＊ levels. Three complexes were obtained. Abnormally, the calculations showed that all the C10--Li14 bond lengths increased obviously but the blue-shift of C10-Li14 stretching frequency occurred after formed complexes. The calculated binding energy with basis set super-position error （BSSE） and zero-point vibrational energy corrections of complexes I-III is -45.757, -35.700 and -39.107 kJ·mol^-1, respectively. The analyses on the combining interaction with the atom-in-molecules theory （AIM） also showed that a relatively strong lithium bond interaction presented in furan homologues C4H4Y-LiCH3 systems. Natural bond orbital theory （NBO） analysis has been performed, and the results revealed that the complex I is formed with n-σ type lithium bond interaction between C4H40 and LiCH3, complex II is formed with TT-s type lithium bond interaction between C4H4O and LiCH3, and complex III is formed with TT-s and n-s type lithium bond interactions between C4H4S and LiCH3, respectively.     

Styrene polymerization catalyzed by nickel complexes bearing hydroxyindanone-iminate ligands

Activated by methylaluminoxane, mononuclear bis（hydroxyindanone-iminate）nickel complexes Ni[ArN=CC2H3（CH3）C6H2（R）O]2 （Ar = 2,6-i-Pr2C6H3, R=Me（1）, R=CI（2）, and R=H（3）） showed good activity for the styrene polymerization. The effect of many reaction parameters including the AI/Ni ratio, temperature, and reaction time on catalytic activities of catalytic systems and the molecular weights of the obrained polystyrene was ascertained. The highest activity of 1.34×10^5g（PS）·mol^-1（Ni）·h^-1 was obtained under the optimum reaction condition. The ^13C NMR spectra of the polymers revealed that the polymer was isotactic-rich atactic polystyrene. And the coordination mechanism was confirmed by the analyses of the polymer chain end-groups.     

二维层状钒氧化合物Co(bpy)(H2O)V2O6的水热合成和晶体结构

采用水热合成法合成了组成为Co(bpy)(H2O)V2O6(bpy=bipyridine)的钒氧化合物,并用红外光谱、元素分析和单晶X-射线衍射等手段对其进行了表征.结果表明:化合物的晶体属于正交晶系,Pca21空间群,a=0.922 3(10)nm,b=1.054 8(12)nm,c=1.439 7(16)nm,V=1.401(3)nm3,Z=4,R1=0.016 4.单晶结构解析表明,化合物具有由钒-氧锯齿链{V2O6}2nn-和n个Co(bpy)(H2O)2 单元通过氧原子共价连接而形成的二维层状结构.