Synthesis and spectroscopic studies of novel Cu(II), Co(II), Ni(II) and Zn(II) mixed ligand complexes with saccharin and nicotinamide

Four novel mixed ligand complexes of Cu(II), Co(II), Ni(II) and Zn(II) with saccharin and nicotinamide were synthesised and characterised on the basis of elemental analysis, FT-IR spectroscopic study, UV–Vis spectrometric and magnetic susceptibility data. The structure of the Cu (II) complex is completely different from those of the Co(II), Ni(II) and Zn(II) complexes. From the frequencies of the saccharinato CO and SO₂ modes, it has been proven that the saccharinato ligands in the structure of the Cu complex are coordinated to the metal ion ([Cu(NA)₂(Sac)₂(H₂O)], where NA — nicotinamide, Sac — saccharinato ligand or ion), whilst in the Co(II), Ni(II) and Zn(II) complexes are uncoordinated and exist as ions ([M(NA)₂(H₂O)₄](Sac)₂).     

固相配位化学反应研究(LXVII)─固－固相反应合成混配化合物

室温或近室温条件下,Co(acac)₂(H₂O)₂与第二配体2,2'-联吡啶、1,10-啡啰啉、8-羟基喹啉、水杨醛肟固相反应得到4个混配化合物,经XRD、IR、UV及元素分析表征了这些产物。     

Synthesis, crystal structure and magnetic properties of a novel complex [Cu(NIT2Py)(PDA)(H2O)]·(CH3OH)(H2O)

A novel complex [Cu(NIT2Py)(PDA)(H₂O)]·(CH₃OH)(H₂O) has been synthesized and structurally characterized by X-ray diffraction methods. It crystallizes in the monoclinic space group P2(1)/c. The structure consists of [Cu(NIT2Py)(PDA)(H₂O)] moiety, one solvent methanol molecule and one water molecule. The copper(II) ion is in a distorted octahedral environment: one nitrogen atom and one oxygen atom from the NIT2Py, one nitrogen atom from the PDA (2,6-pyridine dicarboxylic acid) and one oxygen atom from the aqueous in the basal plane; two oxygen atoms from the PDA in the axial position. The units of [Cu(NIT2Py)(PDA)(H₂O)] were connected as one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the Cu(II) ion and the NIT2Py.     

Solvent effect on La to Nd ion mutation: a Monte Carlo simulation study

A Monte Carlo simulation of statistical perturbation theory (SPT) has been applied to investigate solvent effects on the relative free energies of solvation of La³⁺ to Nd³⁺ ion mutation in several solvents. Comparing the relative free energies for interconversion of La³⁺ to Nd³⁺, in H₂O (TIP3P) from this Letter with computer simulation and experiments, there is good agreement among the three studies, There is also reasonable agreement between calculated structural properties from this Letter and other works. For these ion pairs, the Born's function of the solvents and the differences in solvation dominate the differences in the relative free energies of solvation and partition coefficients.     

Synthesis, characterization and structure of complexes of o-aminophenol-N,N,O-triacetic acid with cobalt(II), nickel(II), manganese(II) and zinc(II)

The potassium salt of o-aminophenol-N,N,O-triacetic acid (APTA) and KMnL·H₂O, KCoL·3H₂O, KNiL·3H₂O, KZnL·3ZH₂O, Co(CoL)₂·7H₂O and Ni(NiL)₂·8H₂O(L³⁻:anion of APTA) have been synthesized and characterized by elementary analysis, thermogravimetric analysis, molar conductance, IR spectra, magnetic measurements and electronic spectra. The coordination environments of these metal ions have been discussed on the basis of these studies. The single crystal structure of cobalt(II)-APTA has been determined as CoL·0.5Co(H₂O)₆·4H₂O, which contains two types of cobalt(II). One type of cobalt(II) is coordinated with six water molecules to form Co(H₂O)₆²⁺, the other is chelated by APTA to form a distorted octahedron and linked into an infinite chain anion [COC₆H₄(OCH₂COO)N(CH₂COO)₂⁻]_n, in which each cobalt(II) atom is linked with neighbouring cobalt(II) atoms through two carboxylate oxygen atoms of the phenoxyacetate group. Water molecules occupy interstices in the structure.     

Spectroscopic Properties of Quercetin Derivatives, Quercetin-3-O-rhamnoside and Quercetin-3-O-rutinoside, in Hydro-organic Mixed Solvents

The characteristic fluorescence properties of quercetin-3- O -rhamnoside (QCRM) and quercetin-3- O -rutinoside (QCRT) were studied in CH₃OH–H₂O and CH₃CN–H₂O mixed solvents. Although QCRM and QCRT are known as nonfluorescent molecules, significant fluorescence emissions were discovered at 360 nm in CH₃OH and CH₃CN when they were promoted to the second excited state. The emission band is broad and structureless and the intensity decreases quickly as the H₂O composition in the solvent increases. When the amount of H₂O exceeds 60% in both mixed solvents, this emission disappears due to the formation of the distorted excited state. This state will be formed due to the strong intermolecular hydrogen bonding between the polar groups of solute and H₂O. As the composition of CH₃OH or CH₃CN in solvent becomes large, the number of molecules having several intramolecular hydrogen bonding increases. Some of these molecules will be changed to a fluorescent species during the decay process, after excitation. The theoretical calculation further supports these results. The change of the lifetimes, quantum yields, and radiative and nonradiative rate constants of molecules was also examined as a function of solvatochromic parameters for CH₃OH–H₂O and CH₃CN–H₂O.     

5-45℃下HCl-KCl-PrOH-H2O体系中HCl的活度系数

我们测定了总离子强度Ⅰ恒定1.0molkg^-1,5-45℃时无液接电池Pt,H₂(1atm)|HCl(m_A),KCI(m_B),PrOH(x),H₂O(1-x)|AgCl-Ag(A)的电动势,其中m_A和m_B分别为HCl和NiCl₂的质量摩尔浓度,x为正丙醇PrOH在混合溶剂中的摩尔分数,x=0.02,0.05,0.08和0.12。     

A multi-responsive luminescent sensor towards Fe_(3+) and acetone based on a Cd-containing metal–organic framework

A Cd-containing metal–organic framework(Cd L), formula as {[Cd_3(L)_2(H_2O)_6] 1.5DMF}, has been synthesized under solvothermal condition by the reaction of 4,40,400-(methylsilanetriyl)tribenzoic acid(H_3L) and Cd~(2+)ion. Single-crystal X-ray diffraction reveals that Cd L displays a three-dimensional framework with 2-fold interpenetration and DMF molecules locate in the void space of the channels. A topological analysis of the framework indicates Cd L is a 3,4-connected pto net. The photoluminescence properties of Cd L are systematically studied in detail. Impressively, Cd L shows excellent detection performance towards Fe~(3+)ion and acetone in the sensing experiments, which undoubtedly demonstrates the great potential of Cd Lasa highly selective multi-responsive luminescent sensor for the detection of organic solvents and metal ions.     

碳氟表面活性剂与碳氢表面活性剂混合水溶液的表面吸附与胶团形成(Ⅳ)——非离子-非离子体系

测定了25℃不同比例的C₁₀F₁₉O(C₂H₄O)₉H与C₈H₁₇C₆H₄O(C₂H₄O)₁₀H混合水溶液的表面张力,研究混合水溶液的表面性质与胶团形成。用两种不同方法计算在表面上的表面成份、分子之间相互作用参数(β_σ)。结果表明,在非离子型碳氟和碳氢表面活性剂混合水溶液中,两种表面活性剂基本上各自形成胶团;表面分子相互作用参数皆为正值;表明此混合体系中碳氟链与碳氢链之间互疏作用的存在。     

Preparations and characterizations of two MOFs constructed with hydroxylphenyl imidazole dicarboxylate

Using the hydrothermal reactions of Mn(Ⅱ) and Ba(Ⅱ) salts with 2-(3-hydroxylphenyl)-1H-imidazole-4,5-dicarboxylic acid(m-OHPhH_3IDC),two novel metal-organic frameworks,namely,{[Mn(mOHPhHIDC)(H_2O)]2H_2O}_n(1) and {[Ba(m-OHPhH_2IDC)_2(H_2O)_3]-2H_2O)_n,(2) have been synthesized and structurally characterized by single-crystal X-ray crystallography,elemental analyses,and IR spectroscopy.Complex 1 features a novel non-interpenetrated three-dimensional(3,4)-connected network with one-dimensional open channels.Complex 2 exhibits a two-dimensional layered structure with rhombic grids.The role of the central metals in the formation of final architectures has been discussed.Furthermore,luminescent and thermal properties of the two complexes have been studied.     

银溶胶体系表面增强拉曼散射光谱的溶剂效应

研究了银溶胶体系表面增强拉曼散射光谱的溶剂效应,发现在不同的溶剂中,银溶胶的聚集状态不同,当胶粒带电荷时,溶剂还能影响分子在胶粒表面的吸附,溶剂通过改变胶粒的聚集状态及分子在胶粒上的吸附这两个因素影响银溶胶体系的SERS光谱。     

溶剂控制的铜基金属-有机框架物的合成与荧光性能

金属-有机框架物在荧光识别领域表现出良好的应用前景,为探究合成更为精确识别的物质,本文利用二羧酸配体(H_2PAIA=5-丙酰胺基间苯二甲酸)和硝酸铜通过溶剂调控合成了两例结构不同的铜基金属-有机框架物(MOFs){[Cu(PAIA)(H_2O)]·2H_2O}(1)和{[Cu_3(PAIA)_2(DMSO)(Pyridine)_(1.5)]}(DMSO:二甲基亚砜;Pyridine:吡啶)(2)。尽管由相同的金属离子和有机配体构筑而成,但显示出具有显著溶剂导向特征的不同框架结构:配合物1为三维NbO型拓扑结构,而配合物2为二维sql型拓扑结构。正是由于这些结构上的差异,导致两个配合物的荧光识别性能和疏水性能展现出显著的不同。配合物1能够同时识别Pb~(2+)和Ag~+离子,而配合物2只能识别Pb~(2+),对Ag~+没有明显的信号响应。配合物1的疏水角85.06°比配合物2的52.71°有显著的增加。     

Molecular, supramolecular structure and catalytic activity of transition metal complexes of phenoxy acetic acid derivatives

Six mononuclear complexes [M(L₁)₂(H₂O)₄] (M = Co(II), 1a and M = Mn(II), 1b), [Cu(L₁)₂(H₂O)₂] (1c), [Cu(L₁)₂(H₂O)(Py)₂] (1d), [Cu(L₃)(H₂O)Cl] · H₂O (3a) and [Co(Sal)(H₂O)(Py)₃] · 2ClO₄ · H₂O (3b) of phenoxyacetic acid derivatives and Schiff base were determined by single crystal X-ray diffraction. The Co(II) (1a) and Mn(II) (1b) complexes are isomorphous. X-ray crystal structural analyses reveal that these coordination complexes form polymeric structure via formation of different types of hydrogen bonding and π-stacking interactions in solid. Thermal analysis along with the powder X-ray diffraction data of these complexes shows the importance of the coordinated and/or crystal water molecules in stabilizing the MOF structure. Complexes 1a, 1c, 3a show marginal catalytic activity in the oxidation of olefins to epoxides in the presence of i-butyraldehyde and molecular oxygen.     

磺胺甲氧哒嗪稀土配合物的合成

在甲醇介质中合成了15种新的磺胺甲氧哒嗪稀土配合物,对它们进行了元素分析、红外光谱、热谱和电导测定,部分配合物还做了X-射线粉末衍射和¹HNMR鉴定。     

稀土元素与天冬氨酸及天冬酰胺的配位作用

本文利用pH电位法在μ=0.10及不同温度下测定l-天冬氨酸和d_。l-天冬酰胺的质子化常数、钇和其它十四个稀土元素与上述配体生成配合物的稳定常数,并研究了水-有机溶剂对天冬氨酸钇稳定性的影响,探讨了钇的位置与“四分组效应”等问题。     

Transfer Gibbs Energies of[Cr(Salen)(H2O)2]BPh4 From Water to Straight-chain Alkanol

Chromium(Ⅲ) is one essential nutrient that has been implicated as glucose tolerant factor(GTF) in the maintenance of normal carbohydrate and lipid metabolism. Schiff base complexes of chromium (Ⅲ) such as N,N' -ethylenebis (Salicylideneiminato) diaquochromium (Ⅲ) chloride[Cr(Salen)(H₂O)₂]Cl as a new kind of GTP model was shown to reduce the symptoms of diabetes significantly, hyperglycemia and cholesterol in diabetic rates^[l]. After studied the decomposition and characterization of[Cr(Salen)(H₂O)₂]Cl^[2], a new confound of[Cr(Salen)(H₂O)₂]BPh₄ is prepared and its transfer Gibbs energies(Δ_tr Go) from water to strait-chain Alkanols is studied in order to understand the thermodynamic properties of[Cr(Salen)(H₂O)₂]⁺ in different solvents.     

Synthesis and structures of three 1-aminoethylidenediphosphonate compounds with transition-metal ions

Three new aminodiphosphonates, namely M(phen)(AEDPH₃)₂·4H₂O (M = Zn, (1); Ni, (2)) and Cu(phen)(AEDPH₃)₂·H₂O (4), in addition to the previously reported Co(phen)(AEDPH₃)₂·4H₂O (3), Cu(2,2′-bipy)(H₂O)(HEDPH₂)·2H₂O (5), and Cu(phen)(H₂O)(HEDPH₂)·2H₂O (6) (AEDPH₄ = 1-aminoethylidenediphosphonic acid, HEDPH₄ = 1-hydroxyethylidenediphosphonic acid, phen = 1,10-phenanthroline and 2,2′-bipy = 2,2′-bipyridyl), have been synthesized and characterized. These compounds are all synthesized at the similar condition (80 °C), whereas they illustrate different frameworks. Compounds 1, 2 and 3 are isomorphous, which contain two same chelate and one six-coordinated metal ion, and display a three-dimensional (3D) supramolecular structure through hydrogen bonds and π–π stacking interactions. Compound 4 contains a chelate and a monodentate , while the Cu ion is five-coordinated. The coordination model of Cu²⁺ in 4 is similar to that of 5 and 6. Comparing with four aminoethylidenediphosphonates, the difference of their structures is directed to the coordination model of the metal ions, while the three copper(II) diphosphonates illustrate different structures based on the deprotonized degree of the corresponding diphosphonic acids.     

Adsorption of cobalt species on the interface, which is developed between aqueous solution and metal oxides used for the preparation of supported catalysts: a critical review

In the present review article, we present the efforts done so far for elucidating the mechanism of adsorption of the Co(II) species, mainly Co(H₂O)₆²⁺, on the interfacial region developed between metal oxide particles, used as catalytic supports, and aqueous electrolytic solutions. Specifically, we present: (i) the principal modes of deposition of the transition metal ionic species (TMIS) on the surface of oxidic supports related with the various methodologies used for the preparation of the supported catalysts; (ii) the state of the art concerning the general aspects of the adsorption mechanisms of the TMIS on the aforementioned interfacial region; and (iii) the works reported so far dealing with the adsorption of the Co(II) species on the surface of γ-Al₂O₃ (γ-alumina), -Al₂O₃ (-alumina), TiO₂ (rutile), and SiO₂ (silica).

It was concluded that the mechanism of adsorption depends on two main factors: on the Co(II) surface concentration and on the nature of the support surface. It seems that, generally, the mechanism changes progressively along the Co(II) surface concentration from the deposition of monodentate–mononuclear inner sphere complexes, weakly evidenced in too low values of the Co(II) surface concentration, to multidentate, multinuclear inner sphere surface complexes at relatively low Co(II) surface concentrations, and then into surface Co(OH)₂-like, eventually mixed precipitates, at relatively high Co(II) surface concentrations but at pH values lower than those required for bulk precipitation. In all cases, Co(II) forms surface species with Co(II) in octahedral symmetry.

However, the exact Co(II) surface concentration values, in which the abovementioned two transitions (concerning the deposited phase) take place, depends on the kind of the support. Thus, SiO₂ favors the formation of the Co(OH)₂-like precipitates even at relatively low Co(II) surface concentrations. In contrast, TiO₂ favors the formation of mononuclear or oligonuclear surface complexes. Finally, alumina, which exhibits the maximum adsorption capacity, favors the formation of highly defected Co(OH)₂-like precipitates, probably mixed Co–Al precipitates.

The exact local structure of the inner sphere Co(II) surface complexes, formed by exchanging the H₂O ligands with surface oxygens, has been already approached but only for the surface planes of the -Al₂O₃ and rutile monocrystals. This structure remains up to now rather unclear for the polycrystalline oxides used as catalytic supports.     

X-ray crystal structure and vibrational spectra of hydrazides and their metal complexes. Part II. Hexaaquacobalt(II)bis(phthalhydrazidato)tetrahydrate

The hexaaquacobalt(II)bis(phthalhydrazidato)tetrahydrate, [Co(H₂O)₆](C₈N₂O₂H₅)₂·4H₂O is examined using single crystal X-ray diffraction analysis. The crystals are triclinic, space group , with a = 9.757(1), b = 10.955(2), c = 11.106(1),  = 100.79(2), β = 90.35(3), γ = 91.54(1) and Z = 2. In [Co(H₂O)₆](C₈N₂O₂H₅)₂·4H₂O, the cobalt(II) is coordinated by six water ligands and the [Co(H₂O)₆]²⁺ is associated with the two O-deprotonated phthalhydrazidato ions only by hydrogen bonds. The infrared and Raman spectra of phthalhydrazide (PH) and infrared spectra of deuterated derivative phthalhydrazide (PD) and of [Co(H₂O)₆](C₈N₂O₂H₅)₂·4H₂O are reported. The theoretical wavenumbers, infrared intensities and Raman scattering activities have been calculated using density functional (B3LYP) method with the 6-311++G(d,p) basis set. The calculated potential energy distribution has proved to be of great help in assigning the spectra PH, its deuterated derivative and [Co(H₂O)₆](C₈N₂O₂H₅)₂·4H₂O. The results from natural bond orbital (NBO) analysis for keto-hydroxy form of PH are presented.     

Syntheses, crystal structures and characterizations of new zinc (II) and lead (II) carboxylate-phosphonates

The syntheses, crystal structures and characterizations of two new divalent metal carboxylate-phosphonates, namely, Zn(H₃L)·2H₂O (1) and Pb(H₃L)(H₂O)₂ (2) (H₅L4-HO₂C–C₆H₄–CH₂N(CH₂PO₃H₂)₂₎ have been reported. Compound 1 features a 1D column structure in which the Zn(II) ions are tetrahedrally coordinated by four phosphonate oxygen atoms from four phosphonate ligands, and neighboring such 1D building blocks are further interconnected via hydrogen bonds into a 3D network. The carboxylate group of H₃L anion remains non-coordinated. Compound 2 has a 2D layer structure. Pb(II) ion is 7-coordinated by four phosphonate oxygen atoms from four phosphonate ligands and three aqua ligands. The interconnection of Pb(II) ions via bridging H₃L anions results in a 001 layer. The carboxylate group of the H₃L anion also remains non-coordinated and is oriented toward the interlayer space. Solid state luminescent spectrum of compound 1 exhibits a strong broad blue fluorescent emission band at 455 nm under excitation at 365 nm at room temperature.