Two Novel Nitrogen-rich Energetic Coordination Compounds M_2(DAT)_5(H_2O)_3(TNR)_2(M = Zn and Co):Synthesis,Characterization,Thermal Properties and Sensitivity

Two novel energetic coordination compounds Zn2（DAT）5（H2O）3（TNR）2 and Co2（DAT）5（H2O）3（TNR）2 were synthesized and their structures were characterized by elemental analysis and FT-IR spectroscopy.The crystal structures were determined by single-crystal X-ray diffraction.The results reveal that the compounds have similar molecular structures and the crystals belong to the triclinic system,space group P with a = 11.491（3）,b = 13.564（3）,c = 15.496（3） ,V = 2180.4（8） 3,C17H28 Zn2N36O19,Mr = 1203.02 g·mol-1,Dc = 1.832 g·cm-3,μ（MoKα） = 1.221 mm-1,F（000） = 1223,Z = 2,R = 0.0596 and wR = 0.1514 for 11289 observed reflections（I 〉 2σ（I）） for Zn2（DAT）5（H2O）3（TNR）2 and a = 11.5291（13）,b = 13.4894（15）,c = 15.4852（17） ,V = 2164.8（4） 3,C17H28Co2N36O19,Mr = 1190.14 g·mol-1,Dc = 1.826 g·cm-3,μ（MoKα） = 0.888 mm-1,F（000） = 1211,Z = 2,R = 0.0576 and wR = 0.1431 for 11218 observed reflections（I 〉 2σ（I）） for Co2（DAT）5（H2O）3（TNR）2,respectively.The thermal decomposition characteristics of the com-pounds were investigated using differential scanning calorimetry and thermal gravimetry-diffediffer-rential thermal gravimetry.The results of thermal decomposition processes were similar for the two compounds.Both undergo four-step decomposition after the loss of coordinated H2O molecules.The final solid residues for the two DAT complexes were the corresponding metal oxides.The kinetic parameter of the first exothermic process of the compounds was studied by applying the Kissinger and Ozawa-Doyle methods.The thermodynamic parameters of the activation could be calculated.Sensitivity tests revealed that Co2（DAT）5（H2O）3（TNR）2 was more sensitive than Zn2（DAT）5（H2O）3（TNR）2.

Synthesis,Crystal Structure and Antitumor Activity of Mixed Ligand Coordination Compound of Copper with Norfloxacin and 1,10-Phen,[Cu(NFLX)(phen)(H2O)]NO3·3H2O

The mixed ligand coordination compound of copper with norfloxacin (NFLX) and 1, 10-phen has been synthesized and characterized by means of X-ray single crystal diffraction. The structure features of the coordination compound are described. Antibacterial activities of the coordination compound have been tested against different microorganisms. The antitumor activities of the coordination compound on leukemia HL-60 cell line and liver cancer BEL-7402 cell line have been measured, respectively. The results indicated that the coordination compound has strong inhibitory effect on HL-60 and BEL-7402 cell lines.

Fluorescence Quenching of a Novel Eu(Ⅲ) Coordination Compound for the Detection of Trace Amounts of Water： Synthesis, Structure and Photoluminescent Property

A novel luminescent coordination compound Eu（TTA）3（DEDAF）（1, TTA = 1,1,1-trifluoro-3-（2-thenoyl）acetone, DEDAF = 9,9-diethyl-4,5-diazafluoren） has been synthesized and fully characterized by infrared spectrum, elemental analysis, UV-vis spectrum, etc. X-ray single-crystal diffraction analysis reveals that compound 1 shows a mononuclear structure with the europium atom in coordinating to one DAF and three TTA ligands. The mononuclear structure units are assembled into a 3-D polymer by hydrogen bonds and π-π interactions. Photoluminescent property of 1 was investigated in detail at room temperature. Complex 1 emits strong red luminescence. However, it could be quenched even by small amount of water. The fluorescence intensity at 614 nm decreases linearly with the water content increasing（vol% in acetonitrile） in the range of 0.025~0.2% under 278 nm excitation. Thermogravimetric analysis has also been studied, which demonstrates good thermal stability of 1.

Europium Coordination Compound with Highly Improved Luminescent Quantum Yield

The luminescent properties of two Eu3＋ compounds based on quinoline-2-car- boxylic acid （Hqc）, [Na2Eu2（qc）6（CH3COO）2（H2O）4].2DMF （1） and [Eu2（qc）6（H2O）6].3H2O （2）, as well as their syntheses and structures are reported. Both compounds are formed by slow evaporation at room temperature and exhibit zero dimensional dinuclear structures. It is worth mentioning that a 4.5-fold enhancement in luminescent quantum yield is achieved by reducing the nonradiative deactivation, through which the quantum yield increases remarkably to 67.62% for 1 compared with 12.18% for 2.

Syntheses, Crystal Structures, Magnetic and Luminescent Properties of Ni(Ⅱ), Cd(Ⅱ) and Pb(Ⅱ) Coordination Compounds Constructed from 5-Fluoronicotinic Acid

Five coordination compounds, namely [Ni2(5-Fnic)2(H2 O)4](1), [Ni(5-Fnic)(μ-5-Fnic)(H2 biim)]n(2), {[Cd((μ-5-Fnic)2(H2 O)2]×4,4’-bipy}n(3), [Pb2(μ-5-Fnic)2(μ3-5-Fnic)2(H2 O)2]n(4), and [Pb(5-Fnic)2(4,4’-bipy)(H2 O)](5), have been constructed hydrothermally using 5-FnicH(5-FnicH = 5-fluoronicotinic acid), H2 biim(H2 biim = 2,2’-biimidazole), 4,4’-bipy(4,4’-bipy = 4,4’-bipyridine), NiCl2×6 H2 O, CdCl2×H2 O and PbCl2. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses(TGA), and single-crystal X-ray diffraction analyses. Structures of 1~5 range from discrete 0 D monomers(1 and 5) to 1 D coordination polymers(2 and 4) and 2 D metal-organic network(3). A broad structural diversity of 1~5 is guided by the type of the metal(Ⅱ) node and the introduction of auxiliary ligands. The magnetic(for 2) and luminescent(for 3~5) properties were also investigated and discussed.

Syntheses, Crystal Structures and Luminescent and Magnetic Properties of Cerium(Ⅲ) and Zinc(Ⅱ) Coordination Compounds Constructed from 3,5-Dibromobenzoic Acid

Two coordination compounds, namely [Ce（3,5-Br2BC）3（3,5-HBrzBC）]n （1） and [Zn（3,5-Br2BC）2（phen）] （2, 3,5-HBr2BC = 3,5-dibromobenzoic acid, phen = 1,10-phenanthroline）, were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a ID chain coordination network, which is further extended into a 3D supramolecular architecture via Br..＇Br and Br＇＂O halogen bonding. Compound 2 consists of a mononuclear molecule, which is assembled to a 3D supramolecular framework through C-H..-O hydrogen bond, π-π stacking interactions and Br..π halogen bonding. Luminescent and magnetic properties of both compounds have also been studied.

The Interaction of Cobalt (Ⅲ) Mixed-Ligand Coordination Compound Containing Dipyrido[3,2-a:2′,3′-c] phenazine With Calf Thymus DNA -

The binding of Co (phen)2dppz3+ to calf thymus DNA,as investigated using absorption spectroscopy. viscosity and electrophoresis measurements,here dppz is dipyrido[3, 2-a: 2'3'-c]phenazine. The compound shows absorption hypochromicity and the specific viscosity increased upon binding to calf thymus DNA The complex is also shown to be more efficient photosensitisers for single strand breaks in plasmid DNA

A New Manganese(Ⅱ) Coordination Compound Constructed by 1,10-Phenanthroline Derivative and Chlorine Anions: Synthesis, Crystal Structure and Theoretical Calculation

The new manganese（Ⅱ） coordination compound, [Mn（Cl）2（L）2]（1, L = 11-fluorodipyrido[3,2-a:2?,3?-c]phenazine）, has been achieved under hydrothermal conditions. The structure of compound 1 was determined by single-crystal X-ray diffraction. 1 crystallizes in monoclinic system, space group C2/c with a = 8.419（2）, b = 12.286（2）, c = 28.451（6） ?, β = 95.889（3）°, V =2927.5（10） ?3, Z = 4, C36 H16 MnF2 Cl2 N8, Mr = 724.41, Dc = 1.644 g/cm3, F（000） = 1460, μ（Mo Ka）= 0.691 mm-1, R = 0.0445 and wR = 0.0982. Adjacent compounds are stacked by one type of π-πinteraction among L ligands to generate a 1D supramolecular chain. Further, the 1D supramolecular chains are stacked by another type of π-π interaction among L ligands to give a 2D supramolecular layer. Moreover, the C-F···π interactions between the carbon atom of the L ligand and the pyrazine ring of the adjacent L ligand further stabilize the supramolecular layer of 1. In addition, natural bond orbital（NBO） analysis has been calculated by the B3LYP/LANL2DZ method, which shows obvious covalent interaction between the coordinated atoms and Mn（Ⅱ） ion.

Ruthenium Coordination Compounds with Polypyridines Ⅶ． Non－intercalative Binding of Ru（Ⅱ） Complexes with Calf Thymus DNA

Two new ruthenium polypyridine complexes. L2RuL2+ where L=2,2'-bipyridine (bpy) and 2, 9-dimethyl-1. 10-phenanthroline (dmp); L' is Schiff base prepared from condensation of 4. 5 diazafluoren-9-one (AFO) and aniline. have been prepared and characterized by elemental analyses, electronic absorption, IR spectra. The binding of the complexes to calf thymus DNA has beeninvestics by absorption. emission spectra and circular dichroism spectroscopy. Experimental results show these two complexes bind to DNA by electrostatic mode and non-interactive binding mode.

STUDIES ON THE SOLID STATE REACTIONS OF COORDINATION COMPOUNDS： LXIX STEPWISE REACTION OF CuCl_2．2H_2O WITH 2，2＇－BIPYRIDYL

Consecutive reaction between two solids, CuCl2.2H2O and 2,2'-bipyridyl in 1:2 molar ratio proceed in tWo steps: the salt first converts to the mediate, then the mediate turns to the final product.

Syntheses of Coordination Compounds of (±)-2-Amino-3-(4-Hydroxyphenyl)Propionic Acid, Mixed Ligand Complexes and Their Biological Activities

Coordination compounds of (±)-2-amino-3-(4-hydroxyphenyl) propionic acid and their mixed ligand complexes with 1,10-phenantroline were synthesized, characterized using electronic and infrared spectral analyses and magnetic susceptibility. The compounds were evaluated for antimicrobial and antioxidant activities. Four different assays were applied for evaluating antioxidant capacity of the compounds. The results obtained indicated a diametric square planar geometry for both cobalt (±)-2-amino-3-(4-hydroxyphenyl) propionic acid complex and its mixed ligand complex. It was suggested that for the binary cobalt(II) complex, the phenolic substituent coordinated with neighbouring central metal ions. However, for the ternary cobalt(II) complex it was suggested it was deprotonated. Octahedral geometry was proposed for both copper complexes. Square planar geometry was indicated for the nickel?(±)-2-amino-3-(4-hydroxyphenyl) propionic acid complex and a mixture of square planar and octahedral geometry for the nickel mixed ligand complex. The cobalt mixed ligand complex elicited the highest activity for all the antioxidant assays. In most cases the binary complexes exhibited better antimicrobial activities relative to their ternary counterparts.

Synthesis Characterization and Biological Activities of an Enamine Derivative and Its Coordination Compounds

The medicinal uses and applications of metal complexes are of increasing clinical and commercial importance;this is as a result of some level of success achieved so far. In this regard, novel enamine free-base ligands were synthesized by the condensation of terephthalaldehyde and 2-(methylamino)ethanol. This afforded a dinegative ONNO donor enamine, free base, characterized using 1H and 13C NMR, Fourier-transformed infrared and UV-vis spectroscopy. Coordination compounds of the enamine were also synthesized using Cu(II), Ni(II), Co(II) and VO(IV) ions. These complexes were characterized by electronic, IR spectrophotometry, mass spectrometry, magnetic susceptibility and EDX. The compounds were thereafter evaluated for their antimicrobial and cytotoxic activities. The data obtained were supportive of an octahedral geometry for the Cu(II) complex, a square-pyramidal geometry for the vanadium complex and a 4-coordinate square-planar geometry for both the cobalt and nickel complexes. The magnetic susceptibility data revealed that the complexes are magnetically dilute and mononuclear with exception of the cobalt complex. The ligands and the complexes did not exhibit significant antimicrobial and cytotoxic assays, indicative of the nontoxicity of the ligand and complexes.

Synthesis,Crystal Structure and Photoluminescent Property of a Novel Dy^(3+) Coordination Compound Containing Rare(H_2O)_(22) Clusters

A novel Dy^（3＋） coordination compound,（H_2pipz）（H_3O）[Dy（pydc）_3]·11H_2O（1,pipz = piperazine and H_2pydc = pyridine-2,6-dicarboxylic acid）,has been hydrothermally synthesized and characterized by X-ray single-crystal diffraction,elemental analysis. It is interesting that the packing structure of compound 1 contains 22-core water clusters. Compound 1 is extended into a threedimensional supramolecular structure via O···H···O hydrogen bonding interactions. Furthermore,the luminescent property of compound 1 was also investigated.

Syntheses, Characterization and Biological Activity of Novel Thiazoylazo Dye and Its Coordination Compounds

The present work describes the synthesis of a novel heterocyclic azo dye by general diazonization of 2-amino-4,5-dimethylthiazole followed by the diazo- coupling of the resulting diazonium ion with 5-methyl-2-(propan-2-yl)phenol to obtain ligand L. This was characterized using Fourier-transformed infrared and electronic spectrophotometry. Ligand L was further coordinated with five metal ions, M:L, 1:2 [M = Cu(II), Mn(II), Zn(II), Ni(II) and Co(II)]. The coordination compounds obtained were characterized by electronic, IR spectrophotometry, magnetic susceptibility and percentage metal analyses. The results obtained suggested that a thiazoylazo dye was obtained as ligand L. It was proposed that two molecules of the solvent coordinated to the metal ion in addition with the ligands to give an octahedral geometry for copper(II), manganese(II) and nickel(II) complexes. On the other hand, square planar geometry was suggested for zinc(II) and cobalt(II) complexes. The anti-infla- mmatory activity of the ligand and coordination compounds was evaluated using four in vitro-based assays viz: xanthine oxidase and lipoxygenase inhibition assay, membrane stability and protein denaturation assay. The synthesized compounds generally exhibited good anti-inflammatory activity in all the assays carried out. However, the reference standards, in this instance, were more effective in the case of xanthine oxidase, lipoxygenase and protein denaturation inhibitory assays. For the membrane stability study, the coordination compounds and ligand L elicited more potent anti-inflammatory activity than the standard drug.

Synthesis, Spectroscopic Characterization and Thermogravimetric Analysis of Cr(Ⅱ), Cu(Ⅱ), Zn(Ⅱ) and Mg(Ⅱ),Captopril Coordination Compounds

In this work,we have reported the synthesis and spectroscopic characterization of captopril(Cap)coordination compounds:Cu(Cap)·2H 2O,Cr(Cap)·H 2O,Zn(Cap)·3H 2O and Mg(Cap)4.Herein,it is worthily mentioned that the FTIR spectroscopic technique was employed to recognized the nature of coordination between captopril ligand and copper,chromium,zinc and magnesium(Ⅱ)metal ions.In view of the infrared spectroscopic tool,the copper(Ⅱ)metal ion coordinated toward captopril drug ligand through sulfur atom of SH group dependent on the absent of stretching vibration band of—SH.Based on this result,the stretching motion ofνa(COO)shifts clearly indicates that Cu 2+,Cr 2+,Zn 2+and Mg 2+the carboxylic group is employed as coordinative site for all compounds as a metal-ligand coordinative bond.As a general behavior,it is verified that the coordination compound thermal stability(considering the release of captopril molecules,not the release of water molecules)is affected by the metal cation radius:minor radius is associated with higher thermal stability,probably due to a higher metal-captopril bond dissociation enthalpy.

Crystal Structure and Characterization of a Novel Neodymium Coordination Compound Based on Dawson Cluster

A new coordination compound, [{Nd(NMP)_2(H_2O)_6Cl}{Nd(NMP)_2(H_2O)_7}H (P_2Mo_(18)O_(62)) (NMP=N-methyl-2-pyrrolidone) was synthesized and characterized by elemental analyses, IR spectrum, and X-ray single crystal structural analysis. The crystal structure indicates that the title compound belongs to monoclinic space group C _c, with unit cell dimensions a =2.4528(5) nm, b =1.9495(4) nm, c =2.4405(5) nm, β =109.94(3)°, Z =4, V =10.970 (4) nm^3, D _c=2.262 g·cm^(-3), R 1=0.0676, wR 2=0.1441. The ESR spectrum of powder of the title compound at 110 K after being exposed to sunlight shows the signal of Mo^(5+), g =1.95. Cyclic voltammetry was measured in aqueous solution containing 0.1 mol·L^(-1) KCl as the supporting electrolyte and shows that the title compound undergoes two one-electron reversible reductions.

Mobile Equilibrium Method for Determining Composition and Stability Constant of Coordination Compounds of the Form M_mR_n

A new method is proposed for determining the composition and stability constant of coordination compounds of the form M m R n ; it can be used to differentiate mono and poly nuclear coordination compounds. The equation derived is lg( A i/(A max - A i) m)=n lg c′ R+lg( m·β(c M/A max ) ( m -1) ). The method is based on Bent French limited logarithm method. The demonstration of the proposed method has yielded correct results for Sc 3+ chlorophosphonazo Ⅲ system and Fe 3+ Chromazurol S system.

Synthesis and Structural Characterization of Mono-and Di-nuclear Zinc(Ⅱ) Coordination Compounds of Triphenylphosphoniopropionate

Two novel coordination compounds of Zn(Ⅱ) with Ph_3P+(CH_2)_2CO-_2(L), namely, [ZnL_4(H_2O)_2]·(ClO_4)_2·2H_2O(compound 1) and [Zn_2Cl_4(μ-L-O,O′)_2](compound 2), have been prepared. The single crystal X-ray structure analysis of these compounds indicates that in compound 1 the Zn(Ⅱ) atom is coordinated by four monodentate carboxylato groups on the equatorial plane and two aqua ligands occupy the axial coordination positions. The pendant oxygen atoms form strong hydrogen bonds with the aqua molecules which results in the stability of this structure. In compound 2, two Zn(Ⅱ) atoms are bridged by a pair of carboxylato groups, showing a skew-bridge mode, and thus enabling a long Zn(Ⅱ)…Zn(Ⅱ) separation. As we know, it is a dinuclear coordination compound with the longest Zn…Zn separation.

Study on the Inert Coordination Compound in the System of“Molybdenum(Ⅵ)—TAE—Hydroxylamine”and its Analytical Application

In the presence of ethyl alcohol or emulsifier OP,molybdenum(Ⅵ) forms 1∶1∶1'water soluble colored coordination com- pound with both of 2-(2-thiazolylazo)-5-diethylaminophenol (abbreviation TAE) and hydroxylamine.This deep blue coordination compound is inert characteristically and remains stable in 1.7 mol/L sulfuric acid,2.4 mol/L hydrochloric or ni- tric acid.It will not be decomposed by masking agents even on boiled,while in that case,almost all the colored coordination com- pounds formed by other metal ions will be decomposed completely.This inert character of the coordination compound of molybdenum(Ⅵ) and its utilization in improving the analytical selectivity have been discussed.In the coexistence of various for- eign ions,especially in the presence of a great quantity of tungsten,which always interferes with the determination of molybdenum,the direct determination of molybdenum in the aqueous solution by applying this system has shown an acceptable sensitivity and reproducibility.From the results of determination in some synthetic and standard samples,it seems feasible to use this system in the determination of molybdenum in nonferrous alloys.

Synthesis, Characterization, Antimicrobial and DNA Binding Studies of a Tetradentate N2O2 Amino Acid Schiff Base and Its Coordination Compounds

Aminoethanoic acid undergoes condensation with 1,4-benzenedicarboxaldehyde to form an O, N, N, O donor Schiff base, N,N'-di(carboxymethylene) terephthalaldehyde, Ligand L. Coordination compounds of this Schiff base using Ni (II), Cu (II), VO (IV) and Co (II) were then obtained in-situ. The Schiff base and the complexes were evaluated for their antimicrobial and DNA binding abilities. Molecular docking studies of the ligand and synthesized compounds were also carried out. Evidence for the formation of the Schiff base coordination compounds and the coordinating atoms was obtained from 1H NMR, infrared and ultraviolet spectral data, EDX, EDTA complexometric titration and magnetic susceptibility measurement. The results obtained are consistent with octahedral geometry for Ni (II) complex, the metal ion coordinating to one molecule of Ligand L and with additional coordination with two oxygen atoms of two molecules of the solvent. A square-planar geometry was suggested for both Co (II), and Cu (II) complexes and a five-coordinate, square pyramidal geometry for the VO (IV) complex. The results further indicated that the carboxylic acid of Ligand L was not deprotonated both in the free base and also the complexes. In addition, the results showed that Compound 2 elicited the best antimicrobial activity potential. Generally, the compounds exhibited considerable good affinity to CT-DNA.