吡啶-2,6-二甲酸衍生物及其Tb(Ⅲ)和Eu(Ⅲ)配合物的合成与荧光性质

以吡啶-2,6-二甲酸(DPA)为起始物,合成了4-羟甲基吡啶-2,6-二甲酸(4-HMDPA)和4-(N,N-二羧甲基氨基)亚甲基吡啶-2,6-二甲酸(4-BMDPA)两种新型多功能配体,并制备了DPA,4-HMDPA及4-BMDPA的Tb(Ⅲ)和Eu(Ⅲ)配合物,对配合物的固体和溶液态的荧光性质进行了研究. 结果表明,在吡啶4位引入弱吸电子基团4-羟甲基会减弱稀土配合物的荧光强度; 在水溶液中稀土配合物与溶液的pH值有着密切的关联,中性水溶液中荧光强度较大; 分子偶极矩较小的溶剂中稀土配合物荧光强度较强. 表明4-BMDPA是较理想的稀土荧光敏化剂.     

Simultaneous spectrophotometric determination of atrazine and cyanazine by chemometric methods

Three novel ligands containing pyridine-2,6-dicarboxylic acid unit, trans-4 -(4'-methoxystyryl) pyridine-2,6-dicarboxylic acid, trans-4-(4'-(dimethylamino)styryl)pyridine-2,6-dicarboxylic acid, and trans-4-(4'-(diphenylamino)styryl)pyridine-2,6-dicarboxylic acid were synthesized and their complexes with Eu(III), Tb(III) ions were successfully prepared. The ligands and the corresponding metal complexes were characterized by means of MS, elemental analysis, IR, (1)H NMR and TG-DTA. The luminescence spectra of Eu(III) and Tb(III) complexes in solid state were studied. The strong luminescence emitting peaks at 615 nm for Eu(III) and 545 nm for Tb(III) can be observed. The applications in cell imaging of the europium and terbium complexes were investigated.     

Macrobicyclic aminals

The synthesis of Schiff base macrocycles in the absence of templating cations and in non-protic and non-coordinating solvent media is reported. The reaction of pyridine-2,6-dicarboxaldehyde with the diamines 1,2-bis(2-aminophenoxy) ethane and 1,4-bis(2-aminophenoxy) butane has been found to give the corresponding macrobicyclic aminals. The chemical properties of the aminals are reported together with a preliminary study of their metal complexation reactions. The X-ray crystal structure of the aminal derived from pyridine-2,6-dicarboxaldehyde and 1,2-bis(2-aminophenoxy) ethane has been determined and verifies the macrobicyclic nature of the product.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

Synthesis and Antibacterial Activity of Novel 5,5′-(Pyridine-2,6-Diyl)bis(4-Arylideneamino-3-Mercapto-1,2,4-Triazole)-Related Derivatives

The reaction of 5,5′-(pyridine-2,6-diyl)bis(4-amino-3-mercapto-1,2,4-triazole) with various aromatic aldehydes in acetic acid yielded the corresponding 5,5′-(pyridine-2,6-diyl)bis(4-arylideneamino-3-mercapto-1,2,4-triazole) derivatives. The structures of the synthesized compounds as well as their intermediates were confirmed by elemental analysis, infrared spectra, ¹H NMR spectra and mass spectra studies. All the synthesized title compounds were screened for their antibacterial activities, and the preliminary results revealed that some of them showed good activities against Escherichia coli and Pseudomonas aeruginosa.     

New octahedral bis-α-diimine nickel(II) complexes containing chloro-substituted aryl groups: Synthesis, characterization and testing as ethylene polymerisation catalysts

Three new 20-electron bis-α-diimine nickel (II) complexes containing chloro-substituted ligands, bis{bis[N,N′-(3-chloro-2-methylphenyl)imino]-1,2-dimethylethane}dibromonickel 2a, bis{bis[N,N′-(3-chloro-2,6-dimethylphenyl)imino]-1,2-dimethylethane}dibromonickel 2b and bis{bis[N,N′-(4-chloro-2,6-dimethyl-phenyl)imino]-1,2-dimethylethane}dibromonickel 2c, were synthesized and characterized. The molecular structure of complex 2a was determined by X-ray crystallography. In the solid state, complex 2a has a pseudo-octahedral geometry about the nickel center, containing two α-diimine ligands in the pseudo-equatorial plane and two trans bromide ligands occupying the axial positions. These complexes, activated by diethylaluminum chloride (DEAC) were tested in the polymerization of ethylene under mild conditions. NMR analysis shows that highly branched polyethylenes are obtained using these bis-α-diimine nickel(II) complexes containing electron-withdrawing Cl groups in the aryl groups (e.g. 84 branches/1000 C, at 20 °C). The catalytic activity, polymer molecular weight and polymer degree of branching were significantly affected by the number of methyl substituents in the ortho-aryl position and the chlorine substituent position in the aryl rings of the coordinated α-diimine ligands.     

Ion recognition properties of new pyridine-2,6-dicarboxamide bearing propeller-like pendant residues: multi-spectroscopic approach

The synthesis and ion binding properties of new amide derived from propeller-like tris(2-pyridyl)amine and 2,6-pyridinedicarboxylic acid chloride were described. Amide binds divalent metal cations: copper(II), nickel(II), zinc(II), and lead(II) in acetonitrile. In acetonitrile:water mixture (9:1 v/v) amide interacts only with copper(II) and nickel(II) cations forming complexes of 1:1 stoichiometry. It was found that the introduction of bulky, nitrogen donor atom bearing pendant groups can influence coordination mode of pyridine-2,6-dicarboxamides. The probable model of ligand-ion interactions is proposed on the basis of 1H NMR and FT-IR spectroscopy.     

Retention behavior of alkali, alkaline earth and transition metal cations in ion chromatography with an unmodified silica gel column

An unmodified silica gel (Develosil 30-5) column (150×4.6 mm I.D.) has been applied to the ion chromatographic separation of alkali, alkaline earth and transition metal cations. The retention behavior of the above cations on the bare substrate was investigated using a number of weak inorganic and organic acid eluents. During this investigation, several separations were achieved and the most suitable eluent conditions were identified. It was concluded that: (a) 1.5 mM HNO₃-0.5mM pyridine-2,6-dicar☐ylic acid eluent was the most effective for the simultaneous separation of common alkali and alkaline earth metal cations, (b) 1.5 mM oxalic acid eluent resulted in the best separation of alkali, alkaline earth, and transition metal cations, (c) 0.5 mM CuSO₄ eluent could be used for the separation of alkali metal cations alone and (d) 0.5 mM ethylenediamine-oxalic acid eluent at pH 5.5 resulted in themost efficient separation of both alkaline earth and transition metal cations.     

Solid-to-Solid Oxidation of a Vanadium(IV) to a Vanadium(V) Compound: Chemisty of a Sulfur-Containing Siderophore

Visible light facilitates a solid-to-solid photochemical aerobic oxidation of a hunter-green microcrystalline oxidovanadium(IV) compound (1) to form a black powder of cis-dioxidovanadium(V) (2) at ambient temperature. The siderophore ligand pyridine-2,6-bis(thiocarboxylic acid), H(2)L, is secreted by a microorganism from the Pseudomonas genus. This irreversible transformation of a metal monooxo to a metal dioxo complex in the solid state in the absence of solvent is unprecedented. It serves as a proof-of-concept reaction for green chemistry occurring in solid matrixes.     

Synthesis, structural, thermal studies and biological activity of a tridentate Schiff base ligand and their transition metal complexes

Schiff base (L) ligand is prepared via condensation of pyridine-2,6-dicarboxaldehyde with -2-aminopyridine. The ligand and its metal complexes are characterized based on elemental analysis, mass, IR, solid reflectance, magnetic moment, molar conductance, and thermal analyses (TG, DTG and DTA). The molar conductance reveals that all the metal chelates are non-electrolytes. IR spectra shows that L ligand behaves as neutral tridentate ligand and bind to the metal ions via the two azomethine N and pyridine N. From the magnetic and solid reflectance spectra, it is found that the geometrical structures of these complexes are octahedral (Cr(III), Fe(III), Co(II), Ni(II), Cu(II), and Th(IV)) and tetrahedral (Mn(II), Cd(II), Zn(II), and UO2(II)). The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, ΔH*, ΔS* and ΔG* are calculated from the DTG curves using Coats-Redfern method. The synthesized ligand, in comparison to their metal complexes also was screened for its antibacterial activity against bacterial species, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus pyogones and Fungi (Candida). The activity data shows that the metal complexes to be more potent/antibacterial than the parent Schiff base ligand against one or more bacterial species.     

Synthesis and Structural Characterization of Some New Magnesium Formamidinates

[Mg(Form)₂(THF)] [Form = bis(2,6‐dimethylphenyl)formamidinate (XylForm) ( 1 ), bis(2,6‐diethylphenyl)formamidinate, (EtForm) ( 2 ), bis(2,6‐diisopropylphenyl)formamidinate (DippForm) ( 3 )] are conveniently synthesized by treating bis(2,6‐dimethylphenyl)formamidine, bis(2,6‐diethylphenyl)formamidine, or bis(2,6‐diisopropylphenyl)formamidine, respectively, with half an equivalent of dibutylmagnesium in THF. Compounds 1 – 3 are mononuclear species in the solid state with five coordinate central metal atoms. The ¹H NMR chemical shift of the formamidinate formyl proton exhibits a correlation with ligand sterics wherein increasing bulk leads to a shift to higher field.     

Stereochemistry of Phosphite Addition to Azomethine Bond of Achiral 2,6-Pyridinedicarbaldimines and Isophthalaldimines—A Comparative Study

Abstract

The addition of dialkyl H-phosphonates to isophthalaldimines 1a–d and pyridine-2,6-dicarboxaldimines 2a–d was investigated and led to the corresponding aminophosphonates. Diastereoselectivity of the addition to pyridine-2,6-dicarboxaldimines was lower than to isophthalaldimines. In contrast, addition of bis(trimethylsilyl) H-phosphonate to both groups of aldimines demonstrated that the diastereoselectivity in case of pyridine-2,6-dicarboxaldimines is comparable or even better than that for the isophthalic derivatives.     

Linear/branched Block Polyethylene Produced by α-Diimine Nickel(Ⅱ)Catalyst and Bis(phenoxy-imine) Zirconium Binary Catalyst System in the Presence of Diethyl Zinc

In order to promote development of linear/branched block polyethylenes based on new catalytic systems,we synthesized a novel α-diimine nickel(Ⅱ) complex with isopropyl substituents on ortho-N-aryl and hydroxymethyl phenyl substituents on para-N-aryl structures.The activity of α-diimine nickel(Ⅱ) catalyst was 3.02×106 g·molNi-1·h-1 at 70 ℃,and resultant polyethylene possessed 135/1000C branches.The linear/branched block polyethylenes were synthesized from ethylene polymerization catalyzed by the α-diimine nickel(Ⅱ) complex/bis(phenoxy-imine) zirconium in the presence of diethyl zinc.With the addition of ZnEt2 (from 0 to 400),the melting peak of resultant polyethylene changed from a single melting peak to bimodal melting peaks.The molecular weights of resultant polyethylene ranging from 26.8 kg/mol to 17.1 kg/mol and PDI values varying gradually from 24.4 to 15.2 were obtained via adjusting ZnEt2 equiv.and molar ratio of two catalysts.In addition,the branching degree of the polyethylene increased from 13/1000C to 56/1000C with the increase of the proportion of α-diimine nickel(Ⅱ) catalyst.Using this binary catalyst system,the reaction temperature of chain shuttling polymerization can be carried out at 70 ℃,which is more conducive to industrial application.     

Resorcinarene Bis‐Thiacrowns: Prospective Host Molecules for Silver Encapsulation

Mixed‐donor atom tetramethoxy resorcinarene bis‐thiacrown hosts, in which the crown unit contains both hard oxygen and soft sulfur donor atoms, were synthesized for soft metal cation binding. The binding properties were investigated both in solution and in the solid state by NMR spectroscopy and X‐ray crystallography. It was found that the resorcinarene bis‐thiacrowns were able to complex silver cations with remarkable affinity forming readily 1:2 host–guest complexes in solution. The solid state structures also revealed that the bis‐thiacrowns form silver complexes in an unanticipated endo‐ and exo‐cavity fashion within the same host molecule. Both the solution and solid state studies indicated the sulfur atoms to be the major contributing donor atoms in forming the binding interactions with silver cations.     

Interaction of different metal ions with carboxylic acid group: a quantitative study

The binding strength of the carboxylic acid group (-COOH) with different divalent metal ions displays considerable variation in arachidic acid (AA) thin films. It is considered that in AA thin films the metal ions straddle the hydrophilic regions of the stacked bilayers of AA molecules via formation of carboxylates. In this study first the uptake of different divalent cations in films of AA is estimated by atomic absorption spectroscopy (AAS). Through the amount of cation uptake, it is found that the strength of binding of different cations varies as Ca2+>Co2+>Pb2+>Cd2+. Variation in the binding strength of different ions is also manifested in experiments where AA thin films are exposed to metal ion mixtures. The higher binding strength of AA with certain metal ions when exposed individually, as well as the preference over the other metal ions when exposed to mixtures, reveal some interesting deviation from the expected behavior based on considerations of ionic radii. For example, Pb2+ is always found to bind to AA much more strongly than Cd2+ even though the latter has smaller ionic radius, indicating that other factors also play an important role in governing the binding strength trends apart from the effects of ionic radii. Then, to get a more meaningful knowledge regarding the binding capability, first-principles calculations based on density functional theory have been applied to study the interaction of different cations with the simplest carboxylic acid, acetic acid, that can result in formation of metal diacetates. Their electronic and molecular structures, cohesive energies, and stiffness of the local potential energy well at the cation (M) site are determined and attempts are made to understand the diversity in geometry and the properties of binding of different metal ions with -COOH group. We find that the calculated M-O bond energies depend sensitively on the chemistry of M atom and follow the experimentally observed trends quite accurately. The trends in M-O bond energies and hence the total M-acetate binding energy trends can actually be related to their molecular structures that fall into different categories: Ca and Cd have tetrahedral coordination; Fe, Ni, and Co exhibit planar 4-fold coordination; and Pb is off-centered from the planar structure (forming pyramidal structure) due to its stereochemically active lone pair of electrons.     

Two-component polymer films of palladium and fullerene with covalently linked crown ether voids: effect of cation binding on the redox behavior

Redox active films have been generated via electrochemical reduction in a solution containing palladium(II) acetate and fulleropyrrolidine with covalently linked crown ethers, viz., benzo-15-crown-5 and benzo-18-crown-6. In these films, fullerene moieties are covalently bonded to palladium atoms to form a polymeric network. Films show ability to coordinate alkali metal cations from the solution. Therefore, in solutions containing salts of alkali metal cations, benzo-15-crown-5-C₆₀/Pd and benzo-18-crown-6-C₆₀/Pd films are doped with cations coordinated by crown ether moiety and anions of supporting electrolyte which enter the film to balance positive charge. These films are electrochemically active in the negative potential range due to the reduction of the fullerene moiety. Reduction of the polymer is accompanied by the transport of supporting electrolyte ions between solution and solid phase. In solution containing alkali metal salts, the process of film reduction is accompanied by the transport of anions from the film to the solution. In the presence of tetra(alkyl)ammonium salts, transport of cations from the solution to the film takes place during the polymer reduction.     

Small‐Molecule Recognition for Controlling Molecular Motion in Hydrogen‐Bond‐Assembled Rotaxanes

Di(acylamino)pyridines successfully template the formation of hydrogen‐bonded rotaxanes through five‐component clipping reactions. A solid‐state study showed the participation of the pyridine nitrogen atom in the stabilization of the mechanical bond between the thread and the benzylic amide macrocycle. The addition of external complementary binders to a series of interlocked bis(2,6‐di(acylamino)pyridines) promoted restraint of the back and forward ring motion. The original translation can be restored through a competitive recognition event by the addition of a preorganized bis(di(acylamino)pyridine) that forms stronger ADA–DAD complexes with the external binders.     

Isokratische, simultane Ionen-Chromatographie von Alkali-, Erdalkali- und anderen Metallionen

Summary A new type of polymer-coated cation exchange column (polybutadiene-maleic acid on silica) recently developed by Kolla/Köhler/Schomburg has been investigated for the separation of up to 18 cations. Seven eluting agents have been studied for their separation effects, namely, tartaric, citric, pyridine-4-carboxylic-, pyridine-2,6-dicarboxylic, phthalic, benzoic and salicylic acid. Ion-exchange and complex formation both have important and sometimes opposing effects on the separation of metal ions.The optimum separating conditions for alkali, alkaline earth as well as Mn and Be ions have been found with a mixture of pyridine-2,6-dicarboxylic and citric acid using conductivity detection. The developed methods have been applied to the analysis of drinking water and wine samples. The detection limits are below 1 mg/l. The relative standard deviations for alkali and alkaline earth ion concentrations between 0.7 and 10 mg/l are in the range 4% to 6% (in Harz water).

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Dank. Wir danken Herrn Dr. G. Schomburg, Max-Planck-Institut für Kohlenforschung, für die überlassung des in seinem Arbeitskreis entwickelten Trennmaterials in Form fertig gepackter TrennsÄulen.     

High efficiency co-sensitized solar cell based on luminescent lanthanide complexes with pyridine-2,6-dicarboxylic acid ligands

Two lanthanide complexes, Ln(HPDA)(3)·4EtOH (Ln = Tb, Dy) (H(2)PDA = pyridine-2,6-dicarboxylic acid, EtOH = ethanol), have been successfully synthesized using hydrothermal or solvothermal methods, and their crystal structures were analyzed by single crystal XRD. Both crystals have orthorhombic symmetry with space group Pbcn, exhibiting three-dimensional (3D) supramolecular architecture through hydrogen bonding interactions. The metal center was coordinated to nine atoms by three pyridine-2,6-dicarboxylic acid ligands. The nine-coordinated lanthanide metal complexes were assembled onto a nanocrystalline TiO(2) film to form co-sensitized photoelectrodes with N719 for dye-sensitized solar cells, and their photoelectrochemical performance was studied. In the tandem structure of composite electrodes, the energy levels of lanthanide metal complexes are reorganized in their single-crystal form, as verified by ab initio calculations. The co-sensitized systems are far superior for electron-injection and hole-recovery compared with single N719-sensitized systems. Luminescence properties were measured and electrochemical analysis was also performed on these complexes.     

Intermolecular hydroamination of oxygen-substituted allenes. New routes for the synthesis of N,O-chelated zirconium and titanium amido complexes

Intermolecular hydroamination of heteroatom-substituted allenes with a bulky arylamine was carried out using a bis(amidate) bis(amido) titanium(IV) complex (1) as a precatalyst. The reaction of 2,6-dimethylaniline with oxygen-substituted allene 2c or 2d in the presence of complex 1 gives the ketimine regioisomer as the exclusive product. Reduction of such ketimine products resulted in the formation of amino ethers that were further employed as proligands for the formation of N,O-chelating five-membered titana- and zirconacycles. Such sterically demanding N,O-chelating ligands result in the high-yielding preparation of mono-ligated products. Solid-state molecular structures of all the complexes revealed distorted trigonal bipyramidal geometry about the metal centers, with a dative bond between the metal and the oxygen donor atom. These new complexes obtained using hydroamination as the key-step in ligand preparation were also shown to be useful cyclohydroamination precatalysts in their own right.     

Poly(amide ester)s from 2,6-pyridinedicarboxylic acid and ethanolamine derivatives: identification of macrocycles by matrix-assisted laser desorption/ionization mass spectrometry

The influence of the polycondensation pathway and aminoalcohol structure was investigated in the synthesis of poly(amide ester)s by polytransesterification from ethyl pyridine-2,6-dicarboxylate and 2-amino-2-methylpropan-1-ol or the corresponding bis(amide alcohol), or by polycondensation from the diacid dichloride. Both linear and cyclic structures were identified by steric exclusion chromatography (SEC) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). Transesterification led to cyclic oligomers (macrocycles) with 2-14 pyridine moities in the ring whereas polycondensation from the diacid dichloride gave low molecular weight polymers (Mn = 1800) and macrocycles.