系列Mn(II)配位超分子的合成、晶体结构和表面光电压研究

采用水热合成方法得到了三种Mn(II)配位超分子: Mn(2,5-dcp)₂(H₂O)₂ (1), Mn(INA)₂(H₂O)₄ (2)和Mn(phen)₂Cl₂ (3) (2,5-dcp＝pyridine-2,5-dicarboxylic acid, INA＝iso-nicotinic acid, phen＝1,10-phenanthroline). 通过X射线单晶衍射、红外光谱(IR)、紫外光谱(UV-Vis)及表面光电压光谱(SPS)等方法对化合物进行了表征. 三种化合物中均存在大量的氢键, 使化合物晶体构成了无限延伸的三维网络结构. 表面光电压谱显示了化合物1～3在300～600 nm范围内呈现出正的光伏响应带, 具有P-型半导体的特征. 讨论了氢键在超分子构建中的作用以及不同配位环境对于配合物表面光电压的影响.     

Solid and solution states studies of two Mn(II) complexes based on N-oxidized pyridine-2,5-dicarboxylic acid

Abstract

Two coordination complexes, [Mn₂(pydco)₂(phen)₂(H₂O)₂]·2H₂O (1) and [Mn(3-pyco)₂(H₂O)₄] (2), based on Mn(II), pyridine-2,5-dicarboxylic acid N-oxide (H₂pydco), and 1,10-phenanthroline (phen) as organic ligands have been synthesized and characterized by elemental analyses, infrared spectroscopy, and single crystal X-ray diffraction. We have synthesized the first Mn(II) complex of H₂pydco. Interestingly, in situ hydrothermal decarboxylation occurred in 2 and (pydco)^2– was totally transformed into pyridine-3-carboxylate N-oxide (3-pyco)^– under hydrothermal conditions. The complexation reactions of these molecules with Mn²⁺ ions were investigated by means of solution studies. The stoichiometry of the most abundant species in the solution (prior to the pH at which precipitation occurs) was very close to that of the corresponding crystalline solid-state complexes.     

Synthesis and crystal structures of two metal-nitroxide complexes including a phenanthroline-substituted nitroxide radical

Two metal-nitroxide complexes, [Cu(IMPhenCOO)(CH₃OH)]₂ ·?(NO₃)₂ (1) and [Co(NIT2Py)(H-2,5-PDA)₂] ·?0.5CH₃OH ·?2H₂O (2) (IMPhenCOOH =?2-carboxyl-9-(4,4,5,5-tetramethylimidazoline-1-oxyl-2-yl)-1,10-phenanthroline, NIT2Py =?2-(2′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and H₂-2,5-PDA =?pyridine-2,5-dicarboxylic acid), have been synthesized and structurally characterized by X-ray diffraction. Complex 1 exists as discrete binuclear molecules and each copper(II) is five-coordinate with one tridentate radical ligand (IMPhenCOOH), the other radical ligand through one carboxyl oxygen and one methanol molecule. Complex 1 is the first structurally characterized complex containing the phenanthroline-substituted nitroxide radical. In 2, the Co(II) is six-coordinate with one radical ligand (NIT2Py) and two bidentate pyridine-2,5-dicarboxylate anions.     

Synthesis,characterization, and biological activity of Cd(II) and Mn(II) coordination polymers based on pyridine-2,6-dicarboxylic acid

The coordination polymers (CPs) {[Cd(Pydc)(H₂O)₃] · PydcH₂} (I) and [Mn(Pydc)(H₂O)₃] · PydcH2} (II) were obtained by the reaction of CdSO₄ · 5H₂O or MnCl₂ · 4H₂O with pyridine-2,6-dicarboxylic acid (PydcH₂). The structures of the CPs I and II were characterized by IR, UV-Vis, TGA, and X-ray single crystal analysis (CIF files CCDC nos. 1417757 (I), 1417758 (II)). The network structures of I and II are constructed by an infinite number of discrete binuclear molecules and free PydcH2. The structures of the CPs I and II connected by the extensive H-bonds and π–π stacking, forming a 3D-network. The CPs I and II were screened to test their antimicrobial activities against different species of bacteria and fungi.     

Cadmium(II), manganese(II) and zinc(II) compounds

Three new compounds, [Cd(μ ₃ -Hpdh)(μ₂-Cl)] _n (1), Mn(Hpdh)₂(H₂O)₂ (2) and Zn(Hpdh)₂ (H₂O)₂ (3) (H₂pdh =?pyridine-2,3-dicarbo-2,3-hydrazide), have been synthesized and characterized by elemental analysis, IR spectra, TG and single-crystal X-ray diffraction. Under hydrothermal conditions, H₂pdh is generated by an in situ acylation of H₂pda (H₂pda =?pyridine-2,3-dicarboxylic acid) with hydrazine hydrate. Complex 1 features a 2D layer structure constructed by a dinuclear Cd(II) building block. In complexes 2 and 3, hydrogen bonding interactions connect mononuclear structures into 3D supramolecular frameworks.     

Synthesis,crystal structure,and density functional theory study of a zinc(II) complex containing terpyridine and pyridine-2,6-dicarboxylic acid ligands: Analysis of the interactions with amoxicillin

An octahedral zinc(II) complex of 2,2′:6′,2″-terpyridine (Tpy) and pyridine-2,6-dicarboxylate (Pydc), [Zn(II)(Tpy)(Pydc)·4H₂O] was synthesized and its structure was determined by a single-crystal X-ray diffraction. The ligand pyridine-2,6-dicarboxylate coordinated to the zinc(II) ion via two pairs of carboxylate oxygens and one nitrogen atom, whereas 2,2′:6′,2″-terpyridine also contributed three coordination bonds through its nitrogen atoms. [Zn(II)(Tpy)(Pydc)·4H₂O] showed luminescence properties between 412 and 435 nm in DMSO. The solid-state octahedral geometry of [Zn(II)(Tpy)(Pydc)·4H₂O] was also preserved in solution as confirmed by the observed UV λ_ex = 346. Experimental and theoretical studies indicated that [Zn(II)(Tpy)(Pydc)·4H₂O] interacted with amoxicillin. Density functional theory calculations at B3LYP/LanL2dz level of theory suggested that [Zn(II)(Tpy)(pydc)·4H₂O] dimer interacts with (2S,5R,6R)-6-{[(2R)-2-amino-2-(4-hydroxyphenyl)-acetyl]amino}-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-24-carboxylic acid (amoxicillin) via highest occupied molecular orbital and lowest unoccupied molecular orbital, π–π interaction, hydrogen bond interaction, and van der Waals forces, thus influencing [Zn(II)(Tpy)(Pydc)·4H₂O] properties.     

New copper(II) complexes including pyridine-2,5-dicarboxylic acid: synthesis,spectroscopic, thermal properties,crystal structure and how these complexes interact with purified PON 1 enzyme

We report the synthesis of two square-pyramidal copper(II) complexes, [Cu(2,5-pydc)(2-aepy)(H₂O)]·H₂O, 1, and [Cu(2,5-pydc)(2-ampy)(H₂O)]·H₂O, 2 (2-aepy = 2-(aminoethyl)pyridine, 2-ampy = 2-(aminomethyl)pyridine, 2,5-pydc = pyridine-2,5-dicarboxylic acid or isocinchomeronic acid). The synthesized complexes have been characterized by X-ray diffraction, FT-IR, elemental, and thermal analysis techniques. The crystal structure of 1 was established by X-ray analysis. Powder X-ray diffraction analysis showed that the complexes are pure. The inhibition of human serum paraoxonase 1 (PON 1, EC 3.1.8.1) enzyme with these complexes were investigated. We used diethyl 4-nitrophenyl phosphate as a substrate to measure the paraoxonase activity of PON 1 enzyme spectrophotometrically. Complexes 1 and 2 decreased the in vitro PON 1 activity with different inhibition mechanisms. Complexes 1 and 2 inhibited paraoxonase activity of this enzyme as competitively and noncompetitively, respectively.     

Crystal structure of a new coordination polymer [LaAg(Pydc)(HPydc)(C2O4)0.5(H2O)2]n (H2Pydc = pyridine-3,5-dicarboxylic acid)

A new 3D coordination polymer, [LaAg(Pydc)(HPydc)(C₂O₄)_0.5(H₂O)₂] _n (I) (H₂Pydc = pyridine-3,5-dicarboxylic acid), has been hydrothermally synthesized and characterized by elemental analyses and single crystal X-ray diffraction. The X-ray diffraction analysis reveals that I (C₁₅H₁₁AgLaN₂O₁₂) crystallizes in triclinic space group P $ \bar 1 $ \bar 1 and features an interesting 3D framework constructed by 2D layers via strong Ag-Ag interactions. Unit cell parameters for I (n = 1): a = 7.749(2), b = 8.316(1), c = 14.239(3) ?, α = 97.64(2)°, β = 100.12(2)°, γ = 94.37(2)°, and Z = 2.     

Synthesis and structural characterization of three supramolecular coordination polymers constructed from different metal ions and 2,2′-bipyridyl-3,3′-dicarboxylic acid

Three new supramolecular coordination polymers based on 2,2′-bipyridyl-3,3′-dicarboxylic acid (H₂BPDC) and Mn(II), Fe(II), and Zn(II) were synthesized under hydrothermal conditions and characterized with single-crystallographic X-ray analysis and IR spectrum. Complex 1 exhibits a 1-D, chain-like structure, which is further connected to 2-D supramolecular layer structure through hydrogen bonds. Complex 2 exhibits a 3-D supramolecular structure constructed from 1-D chains through hydrogen bonds and π–π interactions. Like 1, 3 also shows 2-D supramolecular layer structure based on 1-D chains. Furthermore, the fluorescence of 3 was studied.     

Two manganese(II) complexes constructed from 2-(3-pyridyl)-imidazo[4,5-f] 1,10-phenanthroline and organic dicarboxylates: syntheses,crystal structures,and luminescence

In this study, two new Mn(II) complexes consisting of a phenanthroline derivative and organic acid ligands, [Mn(3-PIP)(1,3-bdc)] _n (1) and [Mn(3-PIP)₂(1,4-bdc)] _n (2) (3-PIP?=?2-(3-pyridyl)-imidazo[4,5-f]?1,10-phenanthroline, 1,3-H₂bdc?=?benzene-1,3-dicarboxylic acid, 1,4-H₂bdc?=?benzene-1,4-dicarboxylic acid), have been synthesized via hydrothermal reaction and characterized by Fourier transform infrared (FT-IR) spectra, elemental analyses, and single-crystal X-ray diffraction. Complex 1 is a one-dimensional (1-D) twisted double chain bridged by 1,3-bdc. The 3-PIP ligands in a parallel fashion are alternately attached to both sides of the 1-D double chain. Complex 2 exhibits a 1-D zigzag chain, to which pairs of crossed 3-PIP ligands are alternately attached. The two complexes are further extended into three-dimensional (3-D) supramolecular structures by hydrogen-bonding and π–π stacking interactions. The N-donor ligands with an extended π-system play a crucial role in formation and stabilization of the final supramolecular frameworks. Thermal properties of 1 and 2 and fluorescence of 2 are investigated in the solid state.     

Complexes of Eu(III), Tb(III) and Cu(II) with proton transfer compound between 2,6-pyridinedicarboxylic acid and 2-aminobenzothiazole: characterization of the structures and physical properties

A proton transfer compound, (ABTH)⁺(PydcH)^? (1), obtained from 2-aminobenzothiazole (ABT) and 2,6-pyridinedicarboxylic acid (Pydc) as well as its Eu(III), Tb(III), and Cu(II) complexes (ABT)₃[Eu(Pydc)₃]·5H₂O (2), (ABT)₃[Tb(Pydc)₃]·5H₂O (3), and (ABT)[Cu(Pydc)(PydcH)]·3H₂O (4) were obtained under ambient conditions and structurally verified by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, powder X-ray diffraction (PXRD), infrared spectroscopy (IR), thermogravimetric analysis (TGA), and magnetic measurements. Compounds 2–4 are the first known solids containing complex anions with Pydc ligands, 2-aminobenzothiazole cations (ABT), and solvate water molecules. During the synthesis of 3, a secondary phase with the formula ABTCl?H₂O was obtained and characterized by elemental analysis and single-crystal X-ray diffraction. The asymmetric unit of 5 consists of six symmetry independent ABT cations, six chlorides, and six water molecules. The two lanthanide complexes showed characteristic emissions of Eu³⁺ and Tb³⁺ ions. The good solubilities of these complexes in water and their luminescence properties make them attractive luminescent labels of biological molecules.     

A new inorganic–organic hybrid compound constructed from polyoxoanions and rare earth coordination complexes

A new chainlike polymer, Na[Ce(dipic)(H₂O)₃]₂ [CrMo₆H₆O₂₄] · 13H₂O (H₂dipic = pyridine-2,6-dicarboxylic acid) (1), has been synthesized and characterized by elemental analysis; IR and XPS spectroscopy, TG analysis, and single-crystal X-ray diffraction. Compound (1) is built up of Anderon-type polyoxoanions as structural motifs and cerium–dipic coordination fragments as linkers to yield an unprecedented one-dimensional chain. Such chains are further in close contact forming a three-dimensional supramolecular framework with channels via extensive hydrogen-bonding interactions among polyoxoanions, dipic ligands and water molecules. Furthermore, the magnetic properties of compound (1) have been studied by measuring their magnetic susceptibility in the temperature range 2–300 K.     

Pyridine-2,5-dicarboxylic acid complexes of nickel(II) with 2,2′-bipyridine and 1,10-phenanthroline coligands; syntheses,crystal structures,spectroscopic and thermal studies

Two pyridine-2,5-dicarboxylic acid (pydcH₂) complexes of nickel(II) with 2,2′-bipyridine and 1,10-phenanthroline were synthesized and characterized by elemental, spectroscopic, thermal analysis, magnetic measurements and single crystal X-ray diffraction techniques. Both [Ni(pydc)(bipy)₂]·7H₂O and [Ni(pydc)(phen)₂]·6.5H₂O crystallize in the monoclinic system and P2₁/c space group. The Ni(II) ions are coordinated by two bidentate bipy or phen ligands and one pydc dianion in a distorted octahedral geometry. The pydc ligand is coordinated through the pyridine nitrogen atom and oxygen atom of carboxyl group as a bidentate ligand. Both carboxylate groups of pydc are deprotonated but only the 2-carboxylate is coordinated to the metal. Thermal decompositions of the complexes have been studied over the range 30–600 °C on heating in a static air atmosphere.     

三个二（有机锡）吡啶-2,3（5）-二甲酸酯的合成、结构和体外抗癌活性

在微波溶剂热中,三环已基氢氧化锡、氧化双（三（（2-甲基-2-苯基）丙基）锡）与吡啶-2,3（5）-二甲酸反应,合成了3个双核二（有机锡）吡啶-2,3（5）-二甲酸酯：Py（CO）₂（SnR₃）₂（MeOH） _n（R：Cy,n=1（1）,2（2）;R：PhCMe₂CH₂,n=0（3））,对它们的组成和结构进行了元素分析、IR、（¹H,¹³C,¹¹⁹Sn） NMR和X射线晶体衍射分析表征,化合物中心锡与配基原子构成畸形四/六面体构型,由于氢键作用,化合物1形成一维链,2形成二维34元大环网状结构。化合物对人结肠癌（HT-29）、肝癌细胞（HepG2）、乳腺癌（MCF-7）、鼻咽癌（KB）和肺癌细胞（A549）的增殖有较强的抑制作用。     

Hydrothermal synthesis,crystal structure and characterization of a 1D neodymium(III) coordination polymer containing the pyridine-2,6-dicarboxylate and oxalate ligands

The reaction of 2,6-pyridinedicarboxylic acid (H₂Pydc) and ammonium oxalate with neodymium(III) nitrate affords the one-dimensional (1D) neodymium coordination polymer formulated as {[Nd₂(Pydc)₂(μ₂-C₂O₄) · 6H₂O] · 2H₂O} _n (I), and characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. The complex presents 1D stair-like chain array bridged through oxalate, and these 1D chains are further linked into 3D supramolecular architecture by extensive intra- and intermolecular hydrogen-bonding interactions. Preliminary magnetic studies reveal the presence of weak antiferromagnetic couplings with the two adjacent magnetic centers bridged through the pyridine dicarboxylate oxygen atom in the complex.     

三个二(有机锡)吡啶-2,3(5)-二甲酸酯的合成、结构和体外抗癌活性

在微波溶剂热中,三环已基氢氧化锡、氧化双(三((2-甲基-2-苯基)丙基)锡)与吡啶-2,3(5)-二甲酸反应,合成了3个双核二(有机锡)吡啶-2,3(5)-二甲酸酯:Py(CO)_2(SnR_3)_2(MeOH)_n(R:Cy,n=1(1),2(2);R:PhCMe_2CH_2,n=0(3)),对它们的组成和结构进行了元素分析、IR、(~1H,~(13)C,~(119)Sn)NMR和X射线晶体衍射分析表征,化合物中心锡与配基原子构成畸形四/六面体构型,由于氢键作用,化合物1形成一维链,2形成二维34元大环网状结构。化合物对人结肠癌(HT-29)、肝癌细胞(HepG2)、乳腺癌(MCF-7)、鼻咽癌(KB)和肺癌细胞(A549)的增殖有较强的抑制作用。     

Synthesis,crystal structure,sensitivity, and effect on thermal decomposition of ammonium perchlorate: an energetic compound Cu(HATZ)(PDA)(H2O)

An energetic coordination compound, Cu(HATZ)(PDA)(H₂O) (HATZ?=?5-aminotetrazole, H₂PDA?=?pyridine-2,6-dicarboxylic acid), has been synthesized and structurally characterized by single crystal X-ray diffraction. Copper(II) was coordinated by two oxygen atoms and nitrogen from PDA, one ring nitrogen of ATZ and one water to form a five-coordinate, distorted square-pyramidal structure. 3-D supramolecular architecture was formed by hydrogen bonding. Thermal decomposition of the compound was examined by DSC and TG-DTG analyses. The kinetic parameters of the first exothermic process of the compound were studied by Kissinger's and Ozawa–Doyle's methods. Sensitivity tests revealed that the compound was insensitive to mechanical stimuli. In addition, the compound was explored as additive to promote thermal decomposition of ammonium perchlorate by differential scanning calorimetry.     

The hydrothermal syntheses, structural characterization of a novel chiral 2-D layer coordination polymer based on pyridine-2,5-dicarbocylic acid (H2Pydc)

A novel chiral 2-D layer coordination polymer [Co(Pydc)(H₂O)₂] · H₂O (Pydc = Pyridine-2,5-dicarboxylate) was hydrothermally synthesized and characterized by elemental analysis, IR spectra and TG analysis. Single-crystal X-ray diffraction shows that Co(1) was connected by the oxygen atom and nitrogen atom of different carboxyls and form a helical-shaped {O(3)-Co-N} _n chain along 2₁ helical axes. The adjacent 1-D {O(3)-Co-N} _n helical-shaped chains are developing along 2₁ helical axes with the same direction and are connected by O(4) to form an ordered 2-D layer. All the molecules exist in the same optical activity that imparts the chiral nature to the whole compound. The text was submitted by the authors in English.     

A new complex constructed by Zn(II) with Pydc and Bipy ligands (H<Subscript>2</Subscript>Pydc = 2,5-Pyridinedicarboxylic Acid,Bipy = 4,4′-bipyridine)

A new complex [Zn₂(Pydc)₂(Bipy)(H₂O)₈] (I) (H₂Pydc = 2,5-Pyridinedicarboxylic Acid, Bipy = 4,4′-bipyridine) was hydrothermally synthesized and characterized by elemental analyses and single crystal Xray diffraction. The X-ray diffraction analysis reveals that I is a discrete binuclear Zn(II) complex and the adjacent binuclear units are further connected together via the strong H-bonding interactions. The article is published in the original.     

Crystal growth,characterization and photoluminescence study of a novel one dimensional coordination polymer of Cd(II) with thiophene-2,5-dicarboxylic acid

A novel one dimensional coordination polymer of Cd(II) with thiophene-2,5-dicarboxylic acid (H₂tdc), {[Cd(tdc) (H₂O)₃]·1.5H₂O}_n has been prepared by gel diffusion method. Elemental analysis, single crystal and powder X-ray diffraction studies, FT-IR and UV–visible spectral studies were used to characterize the title compound. Cd-thiophene units form a linear chain in the crystal structure. Thiophene rings of a linear chain are stacked parallel to each other while the thiophene rings of the adjacent chains are intercalated and stacked ant-parallel to each other. Extensive hydrogen bond formation and π-π interactions between thiophene moieties are responsible for the supramolecular architecture. TG/DTG studies confirm the presence of both lattice and coordinated water molecules. Photoluminescence studies showed that the title compound is red shifted by 46 nm compared to ligand.