Metal-organic frameworks constructed from 2,4,6-Tris(4-pyridyl)-1,3,5-triazine

Five new metal-organic frameworks based on 2,4,6-tris(4-pyridyl)-1,3,5-triazine (tpt) ligand have been hydrothermally synthesized. Reaction of tpt and AgNO 3 in an acidic solution at 180 degrees C yields {[Ag(Htpt)(NO3)]NO(3).4H2O}n (1).Ag(I) is trigonally coordinated by two pyridyl nitrogen and one nitrato oxygen to form a 1D zigzag chain. Reaction of tpt with CuSO4 affords {[Cu2(tpt)2(SO4)2(H2O)2].4H2O}n (2). Copper(II) is bonded to two pyridyl nitrogen, two sulfato oxygen, and two water oxygen atoms to form an elongated octahedral geometry. Each H2O ligand bridges two copper(II), whereas sulfate bridges copper(II) via micro-1,3 and micro-1,1 fashions. The copper(II)-sulfate-H2O2D layers are linked by bidentate tpt to form a 3D polymeric structure. Reaction of Cu(SO4)2, tpt, and 1,2,4,5-benzenetetracarboxylic acid (H4btec) in the presence of piperidine gives [Cu(tpt)(H2btec)1/2]n (3). Copper(I) is located in a trigonal-pyramidal coordination environment and coordinated by three pyridyl nitrogen of tpt in a plane, whereas a carboxylate oxygen is coordinated to the copper(I) axially. The tpt-Cu forms a layer, and the layers are linked through H 2btec2- to form a 2D double-layered coordination polymer. Replacing CuSO4 with ZnI2 in the synthesis gives {[Zn(tpt)(btec)1/2].H2O}n (4). Zinc(II) is in a distorted tetrahedral geometry and linked through bidentate tpt and exotetradentate btec4- to form a 2D coordination grid. Reaction of tpt with CuCN leads to the assembly of a 3D metal-organic framework [Cu3(CN)3(tpt)]n (5). Copper(I) is trigonally coordinated by one pyridyl nitrogen and two cyanides to form an intriguing honeycomb architecture. Luminescence study shows that 1, 3, 4, and 5 have blue fluorescence, which can be assigned to be ligand-centered emissions. Thermal analysis shows that all of these complexes are quite stable, and especially for 4, the framework is stable up to 430 degrees C.     

Effect of impurities on the matrix-assisted laser desorption/ionization mass spectra of insulin.

The effect of impurity (sodium sulfate Na2SO4; copper sulfate CuSO4; potassium ferrocyanide K4Fe(CN)6; and triammonium citrate (NH4)3C6H5O7) concentration on the positive matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) spectra of insulin is described. 2,5-Dihydroxybenzoic acid was used as a desorption matrix. The estimated maximum concentrations of tested salts for which no insulin signal was observed were determined.     

DFT investigation of NH3 physisorption on CuSO4 impregnated SiO2

In this quantum chemical investigation, NH(3) physisorption onto a model of copper sulfate impregnated silica is compared with pure silica and copper sulfate adsorbents. The physisorption process is modeled as direct binding of the NH(3) molecule to the adsorption site of the dry adsorbents and as displacement of a H(2)O molecule by NH(3) in the hydrated complexes. The surface of silica is represented by a hydroxyl group attached to a silsesquioxane cage, H(7)Si(8)O(12)(OH) and silica impregnated with CuSO(4) by the most stable configuration of the cluster containing a CuSO(4) ion pair placed adjacent to the silica cage. H(2)O is systematically added to the dehydrated adsorbents to investigate the role of water in NH(3) adsorption. Modeling hydrated environments of each type of adsorbent is focused on H(2)O molecules that directly coordinate with the active sites. The results indicate that the binding energy of adsorbing NH(3) onto the mixed adsorbent is greater than in pure silica. This enhanced binding in the mixed adsorbent is consistent with improved Br?nsted acidity of the silanol in the presence of CuSO(4).     

Cu/Cu2+沉积型电极在流动酸性电解液中的电化学性能

在流动的高浓度硫酸铜酸性溶液中, 研究了H2SO4浓度、 温度和CuSO4浓度对Cu/Cu2+沉积型电极在石墨基体上电化学性能的影响. 结果表明, 沉积型铜电极反应受控于阴极沉积过程, 室温下动力学过程较慢, 但铜沉积致密, 不易形成枝晶和海绵状铜. 适当提高H2SO4和CuSO4浓度及反应温度可降低铜沉积的极化, 改善其动力学特征; 但Cu离子的溶解度受限于H2SO4浓度, CuSO4浓度提升空间有限. 优化电解液组成为2.5 mol/L H2SO4＋0.7 mol/L CuSO4, 反应温度45 ℃. 在此条件下, 铜在石墨基体上沉积/溶解的交换电流密度提高1个数量级, 具有良好的动力学特征, 单电极充放电电压差降低近50%, 能量效率超过80%.     

结晶水对硫酸铜与丁腈橡胶之间配位交联反应的影响

利用动态力学分析(DMA)、差示扫描量热分析(DSC)、扫描电子显微镜(SEM)、平衡溶胀法、力学性能测试等分析手段, 通过研究五水硫酸铜(CuSO4·5H2O)填充的NBR考察了结晶水对CuSO4与NBR之间配位交联反应的影响. 结果表明, 结晶水的存在可以促进该配位交联反应.     

Thermal analysis and decomposition kinetics of the dehydration of copper sulfate pentahydrate

Journal of Thermal Analysis and Calorimetry - The thermal decomposition kinetics of individual stages of copper sulfate pentahydrate (CuSO4·5H2O) was investigated by TG–DSC, and the...     

CuSO_4/TiO_2催化剂在氨选择性催化还原氮氧化物反应中的性能(英文)

氮氧化物(NO_x)是主要的大气污染物之一.氨气选择性催化还原法(NH_3-SCR)是目前去除固定源排放的氮氧化物的最有效方法,被广泛用于燃煤或者生物质的火电厂中.催化剂是NH_3-SCR法的核心,其中V_2O_5-WO_3/TiO_2催化剂是主要的商业SCR催化剂;但是V_2O_5有毒,对环境的影响很大;另外,该催化剂具有较高的SO_2氧化性能.因而研究者一直在探索新型的SCR催化剂.SO_2是燃煤电厂烟气中的典型气体之一,所以抗硫性能是催化剂的一个重要指标.在SCR反应条件下,SO_2和O_2容易与氧化物催化剂发生反应生成稳定性较高的硫酸盐,覆盖在催化剂表面从而引起催化剂失活.但已有研究发现,硫化会提高K中毒后的V_2O_5-WO_3/TiO_2催化剂的活性.并且,短时间的硫化可以明显提高CuO/Al_2O_3的NH_3-SCR活性.硫酸盐催化剂或许具有较低毒性和较高抗硫性能,应该是一种有前景的SCR催化剂.本文以商业纳米TiO_2为载体,采用湿式浸渍法制备了一系列的CuSO_4/TiO_2催化剂.在自制的活性评价装置上测试了样品的NH_3-SCR活性并且在340℃下连续24 h测试了SO_2、水蒸气及两者共同作用对催化剂活性的影响.使用N_2等温吸附-脱附、X射线衍射(XRD)、X射线光电子能谱(XPS)、H_2程序升温还原(H2-TPR)和NH_3程序升温脱附(NH_3-TPD)对催化剂进行了表征.另外,采用原位红外漫反射光谱研究了CuSO_4/TiO_2催化剂上的NH_3-SCR反应过程.N_2等温吸附-脱附结果表明,负载的CuSO_4没有明显改变载体的孔结构.而XRD结果仅显示锐钛矿TiO_2的衍射峰,说明CuSO_4在载体上有较好的分散度或者CuSO_4的含量低于检测限.XPS结果显示,催化剂中的铜主要以Cu~(2+)形式存在,硫主要以SO_4~(2-)形式存在,而氧主要以晶格氧和吸附氧两种形式存在,并且CuSO_4的存在会增加催化剂中吸附氧的含量.H_2-TPR结果表明,随着CuSO_4含量的增加,催化剂的氧化还原能力逐渐增强.NH_3-TPD结果表明,催化剂表面的酸性位数目随着样品中CuSO_4含量的增加而增加.纯TiO_2的NH_3-SCR活性很差,当温度从300℃增加到450℃时,最高NO_x转化率仅为32.7%.但当CuSO_4负载到TiO_2上以后,催化剂活性明显提高.在反应温度高于340℃时,CuSO_4/TiO_2催化剂的NO_x转化率在94%以上,与商业V_2O_5-WO_3/TiO_2催化剂相当,并且其N_2O生成量低于商业催化剂.不过,当温度低于340℃时,CuSO_4/TiO_2催化剂的NO_x转化率明显低于商业催化剂,说明CuSO_4/TiO_2催化剂的活性仍有待改善.连续24 h测试了SO_2、水蒸汽及两者的共同作用对CuSO_4/TiO_2催化剂活性的影响.结果显示,单独的水蒸气会导致活性轻微下降,但SO_2以及两者共同存在时对催化剂的活性基本没有影响.CuSO_4/TiO_2催化剂的NH_3吸附红外光谱表明,催化剂上存在Lewis和Bronsted两种酸性位,但Bronsted酸性位上的NH_4~+稳定性较差,280℃时即基本消失.在高温时,NH_3主要吸附在Lewis酸性位上且CuSO_4/TiO_2催化剂对NO_x的吸附能力较差,红外光谱未检测到NO_x的吸附峰.380℃下,当NO和O_2通入预吸附NH_3的催化剂样品时,属于Lewis酸性位上NH_3的红外峰明显下降,说明Lewis酸性位上吸附的NH_3参与了反应.CuSO_4/TiO_2显示出高的抗硫抗水性能和比较好的NH_3-SCR活性,应该是一种有应用前景的SCR催化剂.CuSO_4可以增加催化剂的酸性位数目和吸附氧量.根据原位红外漫反射结果,CuSO_4/TiO_2上的SCR反应遵循Eley-Rideal机理.气相的NO与吸附在Lewis酸性位上的NH_3反应生成N_2和H_2O或许是主要的反应途径,并且吸附氧可能会促进这个过程.     

A 3-D noninterpenetrating diamondoid network of a decanuclear copper(I) complex

The solvothermal reaction of CuCl(2).2H(2)O with pyridine-4-thiol and ethanol yielded a novel photoluminescent 3-D polymeric complex with an interesting decorated diamondoid network that is constructed of decanuclear copper(I) cluster units and mu(4)-Cl ligands. The in situ generation of CuSO(4).5H(2)O implies the spontaneous occurrence of desulfurization and redox reactions in the present system.     

Characterization of oxygen dynamics in ZrW2O8

The dynamics of oxygen motion in ZrW(2)O(8) have been characterized using (17)O solid-state NMR. Rates of dynamic exchange have been extracted from magnetization transfer experiments over a temperature range of 40 to 226 degrees C, and distinct values for the associated activation barrier have been observed on either side of the order/disorder phase transition at approximately 175 degrees C. A detailed model for the dynamical process is proposed, which reconciles the observation of continuing oxygen dynamics in the low-temperature phase with the static order implied by earlier X-ray diffraction studies.     

Ferromagnetism in malonato-bridged copper(II) complexes. Synthesis,crystal structures,and magnetic properties of [[Cu(H2O)3][Cu(mal)2(H2O)]]n and [[Cu(H2O)4]2[Cu(mal)2(H2O)]][Cu(mal)2(H2O)2][[Cu(H2O)4][Cu(mal)2(H2O)2][(H2mal = malonic acid)

Three malonato-bridged copper(II) complexes of the formulas [[Cu(H2O)3][Cu(C3H2O4)2(H2O)]]n (1), [[Cu(H2O)4]2[Cu(C3H2O4)2(H2O)]] [Cu(C3H2O4)2(H2O)2][[Cu(H2O)4][Cu(C3H2O4)2(H2O)2]] (2), and [Cu(H2O)4][Cu(C3H2O4)2(H2O)2] (3) (C3H2O4 = malonate dianion) have been prepared, and the structures of the two former have been solved by X-ray diffraction methods. The structure of compound 3 was already known. Complex 1 crystallizes in the orthorhombic space group Pcab, Z = 8, with unit cell parameters of a = 10.339(1) A, b = 13.222(2) A, and c = 17.394(4) A. Complex 2 crystallizes in the monoclinic space group P2/c, Z = 4, with unit cell parameters of a = 21.100(4) A, b = 21.088(4) A, c = 14.007(2) A, and beta = 115.93(2) degrees. Complex 1 is a chain compound with a regular alternation of aquabis(malonato)copper(II) and triaquacopper(II) units developing along the z axis. The aquabis(malonato)copper(II) unit acts as a bridging ligand through two slightly different trans-carboxylato groups exhibiting an anti-syn coordination mode. The four carboxylate oxygens, in the basal plane, and the one water molecule, in the apical position, describe a distorted square pyramid around Cu1, whereas the same metal surroundings are observed around Cu2 but with three water molecules and one carboxylate oxygen building the equatorial plane and a carboxylate oxygen from another malonato filling the apical site. Complex 2 is made up of discrete mono-, di-, and trinuclear copper(II) complexes of the formulas [Cu(C3H2O4)2(H2O)2]2-, [[Cu(H2O)4] [Cu(C3H2O4)2(H2O)2]], and [[Cu(H2O)4]2[Cu(C3H2O4)2(H2O)]]2+, respectively, which coexist in a single crystal. The copper environment in the mononuclear unit is that of an elongated octahedron with four carboxylate oxygens building the equatorial plane and two water molecules assuming the axial positions. The neutral dinuclear unit contains two types of copper atoms, one that is six-coordinated, as in the mononuclear entity, and another that is distorted square pyramidal with four water molecules building the basal plane and a carboxylate oxygen in the apical position. The overall structure of this dinuclear entity is nearly identical to that of compound 3. Finally, the cationic trimer consists of an aquabis(malonato)copper(II) complex that acts as a bismonodentate ligand through two cis-carboxylato groups (anti-syn coordination mode) toward two tetraaqua-copper(II) terminal units. The environment of the copper atoms is distorted square pyramidal with four carboxylate oxygens (four water molecules) building the basal plane of the central (terminal) copper atom and a water molecule (a carboxylate oxygen) filling the axial position. The magnetic properties of 1-3 have been investigated in the temperature range 1.9-290 K. Overall, ferromagnetic behavior is observed in the three cases: two weak, alternating intrachain ferromagnetic interactions (J = 3.0 cm-1 and alpha J = 1.9 cm-1 with H = -J sigma i[S2i.S2i-1 + alpha S2i.S2i+1]) occur in 1, whereas the magnetic behavior of 2 is the sum of a magnetically isolated spin doublet and ferromagnetically coupled di- (J3 = 1.8 cm-1 from the magnetic study of the model complex 3) and trinuclear (J = 1.2 cm-1 with H = -J (S1.S2 + S1.S3) copper(II) units. The exchange pathway that accounts for the ferromagnetic coupling, through an anti-syn carboxylato bridge, is discussed in the light of the available magneto-structural data.     

The effect of copper on the precipitation of scorodite (FeAsO4·2H2O) under hydrothermal conditions: evidence for a hydrated copper containing ferric arsenate sulfate-short lived intermediate

The effect of copper sulfate on scorodite precipitation and its mechanism of formation at 150 °C was investigated. Scorodite was determined to be the dominant phase formed under all conditions explored (0.61 < Fe(III)/As(V) < 1.87, 0.27-0.30 M Fe(SO(4))(1.5), 0-0.3 M CuSO(4), 0-0.3 M MgSO(4), at 2.5 h and 150 °C). The produced scorodite was found to incorporate up to 5% SO(4) and ≤1% Cu or Mg in its structure. The precipitation of scorodite was stoichiometric, i.e. the Fe/As molar ratio in the solids was equal to one independent of the starting Fe/As ratio in the solution. The presence of excess ferric sulfate in the initial solution (Fe/As>1) was found to slow down the ordering of the H-bond structure in scorodite. Precipitation under equimolar concentrations (As = Fe = Cu = 0.3 M), short times and lower temperatures (30-70 min and 90-130 °C) revealed the formation of a Cu-Fe-AsO(4)-SO(4)-H(2)O short lived gelatinous intermediate that closely resembled the basic ferric arsenate sulfate (BFAS) type of phase, before ultimately converting fully to the most stable scorodite phase (96 min and 138 °C). This phase transition has been traced throughout the reaction via elemental (ICP-AES, XPS), structural (PXRD, TEM) and molecular (ATR-IR, Raman) analysis. ATR-IR investigation of an arsenic containing industrial residue produced during pressure leaching of a copper concentrate (1 h and 150 °C) found evidence of the formation of an arsenate mineral form resembling the intermediate basic ferric arsenate sulfate phase.     

COORDINATION CROSSLINKING OF NITRILE RUBBER FILLED WITH COPPER SULFATE PARTICLES

By incorporating copper sulfate(CuSO_4)particles into acrylonitrile butadiene rubber(NBR)followed by heat pressing,a novel vulcanization method is developed in rubber through the formation of coordination crosslinking.This method totally differs from traditional covalent or non-covalent vulcanization approaches of rubber.No other vulcanizing agent or additional additive is involved in this process.By analyzing the results of DMA,XPS and FT-IR,it is found that the crosslinking of CuSO_4 particles filled NBR was induced by in situ coordination between nitrogen atoms of nitrile groups (-CN)and copper ions(Cu~(2 ))from CuSO_4.SEM and EDX results revealed the generation of a core(CuSO_4 solid particle)- shell(adherent NBR)structure,which leads to a result that the crosslinked rubber has excellent mechanical properties. Moreover,poly(vinyl chloride)(PVC)and liquid acrylonitrile-butadiene rubber(LNBR)were used as mobilizer to improve the coordination crosslinking of CuSO_4/NBR.The addition of PVC or LNBR could lead to higher crosslink density and better mechanical properties of coordination vulcanization.In addition,crystal water in CuSO_4 played a positive role to coordination crosslinking of rubber because it decreased the metal point of CuSO_4 and promoted the metal ionization.     

A study of the complexation and extraction of Cu(II) sulfate and Ni(II) sulfate by N3O2-donor macrocycles

Comparative solvent extraction (water/chloroform) studies of Ni(II) and Cu(II) employing a dinonyl-substituted N3O2-donor macrocycle (L2) as extractant have been undertaken from sulfate, chloride, nitrate and acetate-containing aqueous media. Contrary to expectations, efficient extraction of both metal sulfates was observed, the degree of extraction being comparable (or slightly enhanced) relative to that observed for each of the other anionic systems. X-Ray diffraction studies of [NiL1(H2O)3]SO4 x 4H2O and [CuL1(H2O)]SO4 x 6.67 H2O (where L1 is the unsubstituted derivative of L2) show that each complex occurs as a hydrogen-bonded 'cluster', with the sulfate anions involved in hydrogen bonded networks that incorporate ligand amine protons and water molecules; in the copper complex, which adopts a dimeric arrangement, simultaneous sulfate binding to a copper site is also present. In each complex the macrocyclic ligand fails to coordinate via its ether oxygen donors but instead is arranged so that the metal ion and sulfate anions are somewhat shielded hydrophobically from the exterior of the complex cluster assembly.     

Thermal degradation of acetate-intercalated hydroxy double and layered hydroxy salts

Two hydroxy double salts (HDSs), zinc copper hydroxy acetate (ZCA) and zinc nickel hydroxy acetate (ZNA), and an analogous layered compound, zinc hydroxy acetate (ZHA), have been prepared by a coprecipitation method. The thermal degradation of these materials was characterized via thermogravimetric analysis (TGA), differential thermal analysis (DTA), and TGA coupled with Fourier transform infrared spectroscopy of gas-phase products, TGA-FTIR. Loss of physisorbed and interlayer H2O was observed between 50 and 150 degrees C for all compounds. Acetic acid, acetone, water, and CO2 were released at high temperatures with relative acetone yields found to be dependent on precursor identity, with very little formed from ZCA compared with ZHA and ZNA. Combined FTIR and XRD analysis of solid residues extracted at different points in the heating profile suggests that ketonization occurs via dissociative adsorption of acetic acid on ZnO surfaces. Nanometer-sized ZnO particles were formed from ZHA, showing slight preferential growth in the ZnO (002) lattice direction, while the presence of a second metal, Ni or Cu, served to retard ZnO crystallite growth at temperatures below 600 degrees C and eliminate preferential growth. ZCA leads to the formation of reduced copper species (metallic copper and Cu2O) when heated to 250 degrees C.     

Hydro(solvo)thermal Construction of a Copper Coordination Polymer Involving in Situ Ligand Synthesis: Preparation and Structure of [Cu_3(bdcO)_2(H_2O)_2]_n

1 INTRODUCTION Increasing attention has been paid to the coppercoordination polymer frameworks not only due totheir intriguing structure diversity but also theirpotential applications in the areas of molecular ad-sorption, catalysis, electromagnetism and photo-chemistry[1～4]. Incorporation of both organic and in-organic components in these compounds has createda new direction in searching for functional materialswith desired structures and properties. Over the lastdecades, the majority o…     

New and clean strategy for the determination of Cu2+ in electroless copper plating baths

This article concerns a new and clean strategy for the determination of Cu(2+) in electroless copper plating baths with differential spectrophotometry. With this strategy, the problem of too high absorbance of Cu(2+) under plating conditions has been solved. We investigated the influence of copper sulfate, sodium hypophosphite, nickel sulfate, sodium citrate, polyglycol, temperature and pH on the absorption spectrum of Cu(2+) in electroless copper plating baths. Five grams per litre of CuSO(4).5H(2)O solution was selected as the reference solution. Experimental results prove that, this strategy has the merits of fast and high accuracy compared to the traditional techniques. Linearly dependent coefficient of the working curve is 0.9999 and the components in the formula have no obvious effect on the detection of Cu(2+) under experimental conditions. Therefore, we can directly move solutions from the EC plating baths for detection, after that the sample can still go back to the baths without any pollution from the plating process to the environment.     

Synthesis, structure and spectral investigation of hydrogen bonded helical chain in mixed ligand Cu(II) pyrimidone complex

A simple mono-aqua-dichloro copper(II) pyrimidone complex has been synthesized and characterized using various spectral techniques such as Infrared and Raman in addition to the single crystal X-ray diffraction. The single crystal X-ray analysis carried out for the complex under study brings out the fact that there are two molecules in the unit cell with parameters a = 9.657(2); b = 3.857(2); c = 10.781(2); alpha = 90 degrees; beta = 107.781 degrees; gamma = 90 degrees; V = 382.891 and are crystallized in monoclinic crystal system with Pn space group. In solid state the molecules are interconnected through strong hydrogen bonding [O4...H21-O2W = 2.644 angstroms; O4...H21 = 1.853 angstroms; angleO4...H21-O2W = 172.87 degrees;] formed between the coordinated water molecule (O2W) and the exocyclic ketonic oxygen of the pyrimidone ring (O4). This H-bonding interaction causing a twist in the C1=O1...H21 segment [angleC1=O1...H21 = 122.29 degrees] in combination with weak pi-pi stacking interaction (3.857 angstroms) of the adjacent pyrimidone rings brings the single stranded helical chain which possesses both P and M sense of supramolecular helical assembly. The internal and external modes of vibrations of the crystal under study have been estimated and discussed by applying group theoretical methods.     

Synthesis and X-ray Powder Structures of Two Lamellar Copper Arylenebis(phosphonates)

Reaction of copper salts with 1,4-phenylenebis(phosphonic acid) yielded a conventional layered compound, Cu(2)[(O(3)PC(6)H(4)PO(3))(H(2)O)(2)], while a similar reaction with 4,4'-biphenylenebis(phosphonic acid) resulted in a new lamellar structure with composition Cu[HO(3)P(C(6)H(4))(2)PO(3)H]. The structures of these compounds were solved ab initio by using X-ray powder diffraction data. The crystals of the phenylenebis(phosphonate) compound are monoclinic, space group C2/c, with a = 18.8892(4) ?, b = 7.6222(2) ?, c = 7.4641(2) ?, beta = 90.402(2) degrees, and Z = 4. The layer structure in this case is similar to that in copper phenylphosphonate, Cu[O(3)PC(6)H(5)]. The metal atoms display a distorted square pyramidal geometry where four of the coordination sites are occupied by the phosphonate oxygens. The remaining site is filled by an oxygen atom of the water molecule. Adjacent metal-O(3)PC layers are covalently pillared by the phenyl group of the phosphonates to create a 3-dimensional structure. Cu[HO(3)P(C(6)H(4))(2)PO(3)H] is triclinic, space group P&onemacr;, with a = 4.856(2) ?, b = 14.225(5) ?, c = 4.788(2) ?, alpha = 97.85(1) degrees, beta = 110.14(1) degrees, gamma = 89.38(1) degrees, and Z = 1. The structure in this case, ideally consists of linear chains of copper atoms. The copper atoms are bridged by centrosymmetrically related phosphonate groups utilizing two of their oxygen atoms. This binding mode leads to square planar geometry for the copper atoms. The third oxygen atom of the phosphonate is protonated and is involved in linking adjacent linear chains through hydrogen bonds. At the same time, these hydroxyl oxygens interact weakly (Cu-O = 3.14 ?) with the copper atoms of the adjacent chain. Considering these long Cu-O interactions, the geometry of the copper atom may be described as distorted square bipyramidal. As in the phenylphosphonate structure, the biphenyl groups covalently link the Cu-O(3)PC networks in the perpendicular direction.     

Syntheses, crystal structures and properties of novel copper(II) complexes obtained by reactions of copper(II) sulfate pentahydrate with tripodal ligands

Three novel metal-organic frameworks (MOFs), [Cu(1)SO4].H2O (4), [Cu2(2)2(SO4)2].4H2O (5) and [Cu(3)(H2O)]SO4.5.5H2O (6), were obtained by hydrothermal reactions of CuSO4.5H2O with the corresponding ligands, which have different flexibility. The structures of the synthesized complexes were determined by single-crystal X-ray diffraction analyses. Complex 4 has a 2D network structure with two types of metallacycles. Complex 5 also has a 2D network structure in which each independent 2D sheet contains two sub-layers bridged by oxygen atoms of the sulfate anions. Complex 6 has a 2D puckered structure in which the sulfate anions serve as counter anions, which are different from those in complexes 4 (terminators) and 5 (bridges). The different structures of complexes 4, 5 and 6 indicate that the nature of organic ligands affected the structures of the assemblies greatly. The magnetic behavior of complex 5 and anion-exchange properties of complex 6 were investigated.     

A universal empirical expression for the isotope surface exchange coefficients (k*) of acceptor-doped perovskite and fluorite oxides

The isotope surface exchange coefficient k* determined in an 18O/16O exchange experiment characterises the exchange flux of the dynamic equilibrium between oxygen in the gas phase and oxygen in a solid oxide. At present there is no atomistic expression that relates measured exchange coefficients to materials' parameters. In this study an empirical, atomistic expression is developed that describes the exchange kinetics of gaseous oxygen with diverse acceptor-doped perovskite and fluorite oxides at temperatures above T approximately 900 K. The expression is used to explain the observed correlations between surface exchange coefficients k* and oxygen tracer diffusion coefficients D* and to identify compounds that exhibit high surface exchange coefficients.