Synthesis and Antitumor Activity of 3-[2-(4-Hydroxy-Phenyl)-Ethyl]-Benzo[d] Isoxazole-4,6-Diol

A new phloretin derivative 1 3-[2-(4-hydroxy-phenyl)-ethyl]-benzo[d] isoxazole-4,6-diol (yield 63%) was synthesized from phloretin by carbonyl nucleophilic addition condensation reaction. Its structure was characterized by 1H NMR, 13C NMR and HR-MS. The phloretin, compound 1, resveratrol and acetylated resveratrol were determined by comparing them with paclitaxel. Anti-tumor activity of alcohol on SPC-A1, EC109, A549, MCF-7 and MDA-MB-231 cell lines. Compound 1 showed better antitumor activity than docetaxel against A549 tumor cells.

Hydrothermal Syntheses and Crystal Structures of Six Complexes Constructed from 1,3,5-Benzenetricarboxylic Acid and 4'-(4-Pyridyl)-2,2':6',2''-terpyridine Mixed Ligands

Six new transition metal complexes, [Zn（HBTC）（PYTPY）]n·n PYTPY（1）, [Cu（HBTC）（PYTPY）]n·n PYTPY（2）, [Co（HBTC）（PYTPY）]n·n DMF（3）, [Mn（HBTC）（PYTPY）]n·n DMF（4）, [Cd（HBTC）（PYTPY）（H2O）]n·2nH2O（5）, and [Co（HBTC）（PYTPY）（H2O）2]（6）,（H3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4＇-（4-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, DMF = N,N？-dimethylformamide）, have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional（3D） supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.

Syntheses, Structures and Photoluminescence of the Cadmium(Ⅱ) and Copper(Ⅱ) Complexes Based on 4'-(4''-Pyridyl)-2,2':6',2''-terpyridine and 1,4-Benzenedicarboxylic Acid Ligands

Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.

Synthesis of 1-(2-Hydroxyphenyl)-3-Phenyl-1,3-Propanedione and Luminescence Properties of Its Europium Complexes

Using 2＇-Hydroxyacetophenone and as the raw material, 1-（ 2-Hydroxyphenyl ）-3-Phenyl-1, 3- Propanedione （HPPPD） was synthesized by esterification reaction and Fries rearrangement reaction. And the complexes of HPPPD with europium were also synthesized. The compounds were characterized by IR, thermo-gravimetric analysis and ^1H-NMR. The effects of phenolic hydroxyl on the luminescence properties of complexes were studied. The results show that the complexes emit strong red fluorescence and the fluorescence intensity of the ternary complex is better than that of the duality. But the complexes of HPPPD with Sm（ Ⅲ ）, Tb （ Ⅲ ）, Dy （ Ⅲ ） emit weak fluorescence. The phenomenon was interpreted by electron-effect and energy-matching mechanism. Energy transfer mechanism of the luminescence in the complex was discussed.

Syntheses, Characterization and Antitumour Activities of Rare Earth Metal Complexes with 2-(((4,6-dimethyl)-2-Pyrimidinyl)thio)-Acetic Acid

Eight rare earth metal （ Ⅲ ） complexes with 2- （ （（4,6-dimethyl）-2-pyrimidinyl） thio）-acetic acid, LnL3· n H2O [HL = 2-（（（4,6-dimethyl）-2-pyrimidinyl）thio）-acetic acid; Ln = La, Ce, Pr, Nd, Sm Eu, Gd, Tb; n = 4 or 5], were prepared and characterized by elemental analysis, complexometric titration, thermal analysis, conductivity, IR and ^1H- NMR. The results reveal that carboxyl group of the hgand coordinates with rare earth ions in bidentate mode after deprotonated. The water molecules exist as crystal water in the complexes. The anti-tumour activities of HL and some complexes were tested by both the MTT and SRB methods. The results show that the suppression ratios of some complexes against the tested tumour cells （HL-60 human leukemia cell lines, BGC-823 human gastric carcinoma cell lines, hela human cervix adenocarcinoma cell lines and Bel-7402 human hepatic carcinoma cell lines） are superior to HL.

Synthesis, crystal structure, and fluorescence of two dimeric europium(III) complexes with 2-(trifluoromethyl)benzoate

Two complexes [Eu2（2-TFMBA）6（2,2′-bipy）2]·2H2O （1） and Eu2（2-TFMBA）6（1,10-phen）2 （2） （2-TFMBA=2-（Trifluoromethyl） benzoate; 2,2′-bipy=2,2′-bipyridine; 1,10-phen= 1,10-phenanthroline） were synthesized by solvent method and determined by X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system with space group P21/c, whereas complex 2 crystallizes in triclinic system with space group Pi. Both are binuclear molecules with an inversion center. In complex 1, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in bidentate-bridging mode. Each Eu^3＋ ion is eight-coordinated with six O atoms from five 2-TFMBA ligands and two N atoms from one 2,2′-bipy molecule. In complex 2, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in two modes, namely, bidentate-bridging and tridentate-bridging. Each Eu^3＋ ion is nine-coordinated with seven O atoms from five 2-TFMBA ligands and two N atoms from one 1,10-phen molecule. The two complexes both exhibited strong red fluorescence under ultraviolet light, and the ^5D0→^7Fj （j=0-4） transition emissions of Eu^3＋ ion were observed in their emission spectra.

Syntheses, Crystal Structures and Photoluminescence Properties of Cadmium(Ⅱ) and Nickel(Ⅱ) Complexes with 2-(2-Benzimidazolyl)quinoline

Two novel complexes, [Cd2（BMQU）2Cl4] （1） and [Ni（BMQU）2HPO4]·1.5H2O （2） （BMQU = 2-（2-benzimidazolyl）quinoline）, were synthesized by the hydrothermal method and characterized by elemental analysis, IR, and TG-DTG. The crystal structures were determined by single-crystal X-ray diffraction. Both 1 and 2 crystallize in the triclinic system, space group P . The data for 1： a = 0.8342（7）, b = 0.9226（9）, c = 1.0646（8） nm, α = 90.819（2）, β = 97.466（2）, γ = 98.280（2）°. The Cd（Ⅱ） is coordinated with three chlorine atoms and two nitrogen atoms of a BMQU molecule, generating a distorted square-pyramidal geometry. The dinuclear Cd（Ⅱ） complex is formed by two chlorine bridge bonds, and the one-dimensional chain structure is constructed with the hydrogen bond N-H…Cl and π-π stacking interaction. The data for 2： a = 1.2251（1）, b = 1.2451（1）, c = 1.2868（1） nm, α = 107.510（2）, β = 98.630（1）, γ = 109.921（2）°. The Ni（Ⅱ） is coordinated with four nitrogen atoms of two BMQU molecules and two oxygen atoms of a HPO42-, forming a distorted-octahedral geometry. The two-dimensional layer structure is formed by the hydrogen bonds and π-π stacking interaction between neighboring molecules. Complex 1 shows a strong blue fluorescence emission （λmax= 456 nm） at solid state.

SYNTHESIS,CHARACTERIZATION,THERMAL DEGRADATION AND ELECTRICAL CONDUCTIVITY OF OLIGO[2-(THIEN-2-YLMETHYLENE)AMINOPHENOL]AND OLIGOMER-METAL COMPLEXES

The optimum reaction conditions of the oxidative polycondensation of 2-(thien-2-yl-methylene)aminophenol (2-TMAP) has been accomplished by using air O_2,H_2O_2 and NaOCl oxidants in an aqueous alkaline medium between 20℃and 90℃.The structures of the monomer and oligomer were confirmed by FT-IR,UV-Vis,~1H-NMR and ^(13)C-NMR and elemental analysis.TGA-DTA,size exclusion chromatography(SEC) techniques and solubility tests were applied for characterization.The ~1H-NMR and ^(13)C-NMR data show that the polymeriz...

Two Fluorescent Complexes Assembled by Schiff Base 2-Methoxy-6-(phenyliminiomethyl) Phenolate Ligand

Two d10 metal complexes Zn（NCS）2（C14HI3NO2）2 （1） and [Cd（NO3）2（CI4HI3NO2）2]. 4H20 （2） assembled by 2-methoxy-6-（phenyliminiomethyl） phenolate ligand （C14H13NO2, HL） have been synthesized and characterized by elemental analysis, IR and TG The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in monoclinic, P21/c space group with a = 17.321（7）, b = 11.781（0）, c = 15.593（2） A, fl = 110.273（6）°, V = 2984.95 A3, Z = 4, C30H26N404SzZn, Mr = 636.04, F（000） = 1312, Dc = 1.415 g/cm3,μ（MoKa） = 1.004 mm＂1, the final R = 0.0403 and wR = 0.0900 for 21441 observed reflections with I 〉 20（/）. Complex 2 is of monoclinic system, space group C2/c with a = 16.7767（2）, b = 10.8989（2）, c = 17.4928（2） A, fl = 90.614（9）°, V= 3198.37 A3, Z = 4, C28H34N4O14Cd, Mr= 731.25, F（000） = 1528, Dc = 1.568 g＇cm^-3, μ（MoKa） = 0.757 mm-1, the final R = 0.0361 and wR = 0.0857 for 19811 observed reflections with I 〉 2σ（I）. The two complexes were formed by Schiff base 2-methoxy-6-（phenyliminiomethyl） phenolate ligand and formed a 3D supramolecular architecture by π-πstacking interactions. Moreover, the complexes are luminescent in the solid state. These observations indicate that the complexes are promising system for the development of potential photoactive materials.

Synthesis, Characterization and Luminescence of Lanthanide Chloride Complexes with N,N,N',N'-Tetra[(2-benzimidazolyl) methyl]-1,2-Ethanediamine

N,N,N',N'-tetra[(2-benzimidazolyl)methyl]-1,2-ethanediamine (EDTB) lanthanide chloride complexes were prepared (Ln3+=Eu3+, Tb3+ or Gd3+). The results of single crystal X-ray structural analysis show that [(EDTB)GdCl2]Cl(C2H5OH)(H2O)2 crystal is in space group P21 / c with a=8.848(2) ?, b=26.313(5) ?, c=18.929(4) ?, β=97.82(3)o, V=4366(2) ?3, Z=4. The luminescent properties of the terbium and europium complexes have been studied.

Synthesis, Structure and Catalytic Activity of a Manganese(Ⅲ) Complex Based on 2-(2-Hydroxyphenyl)-5,6-dichlorobenzimidazole Ligands

A new ligand, 2-（2-hydroxyphenyl）-5,6-dichlorobenzimidazole, H2pbmCl2（1）, and a novel MnIII complex, [MnIII（HpbmCl2）（pbmCl2）（DMF）2]（2）,（DMF = N,N-dimethylformamide）, have been synthesized and characterized. The crystal of compound 1（C13H8Cl2N2O, Mr = 279.12） belongs to the monoclinic system, space group P21 with a = 3.770（5）, b = 25.20（3）, c = 5.865（7） A, = 92.727（17）o, V = 556.6（12） A3, Z = 2, Dc = 1.665 g/cm^3, S = 1.137, μ= 0.568 mm^-1, F（000） = 284, the final R = 0.0876 and wR = 0.2334 for 1848 independent reflections. The molecule is planar due to the presence of a strong intramolecular hydrogen bond between O–H group of phenol and N atom of imidazole. H2pbmCl2（1） molecules are arranged into a one-dimensional linear chain through intermolecular hydrogen bonds（N–H…O and C–H…Cl）. The crystal of complex 2（C32H27Cl4MnN6O4, Mr = 756.34） belongs to the monoclinic system, space group P21/c with a = 19.043（10）, b = 10.808（5）, c = 18.704（11）A, β= 115.540（6）°, V = 3473（3） A3, Z = 4, Dc = 1.446 g/cm^3, S = 1.3, μ = 0.733 mm-1, F（000） = 1544, the final R = 0.1219 and wR = 0.2681 for 7811 independent reflections. The Mn ion adopts a distorted octahedral geometry coordinated by two deprotonated H2pbmCl2 ligands and two DMF molecules. The [MnIII（HpbmCl2）（pbmCl2）（DMF）2] molecules are arranged into a three-dimensional structure through hydrogen bonds（N–H…N, C–H…N and C–H…Cl） and weak π···πinteractions. The activity measurements suggest that complex 2 is able to serve as a catalyst for H2O2 disproportionation reaction to form O2 in neutral water solution.

The First Example of a Supramolecular Structure Containing [2-(1H-Pyrazol-3-yl)-pyridine] Complex and both α-and β-Octamolybdates

The title compound, [Ni（C8N3H7）3]4[Mo8O26]2·6H2O 1, has been synthesized from the reaction of 2-（1H-pyrazol-3-yl）-pyridine （L） with （NH4）2MoO4·2H2O and NiCl2·6H2O. Elemental analysis, IR, UV spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of the compound. Crystal data： C96H96Mo16N36Ni4O58, Mr = 4451.97, monoclinic system, space group P21/n, a = 20.846（5）, b = 14.825（5）, c = 23.122（5） A ,β= 91.594（5）°, V = 7143（3）A^3, Z = 2, F（000） = 4344, Dc = 2.070 g/cm^3,μ = 1.968 mm^-1, R = 0.0452 and wR = 0.1056 for 17102 independent reflections （Rint = 0.0442） and 11074 observed reflections （I 〉 2σ（I））. Structural analysis indicates that two kinds of octamolybdates （[α-Mo8026]^4- and [β-Mo8026]^4-） co-exist in the compound. This is the first example of a supramolecular structure containing L complex as well as both α- and β-octamolybdate clusters.

Synthesis,Crystal Structure and Antitumor Activity of a Novel Zn(Ⅱ)Complex with 2-(Nicotinoyloxy)acetic Acid Ligand

A novel Zn（Ⅱ） complex, [ZnL2（H2O）4]·H2O（1, HL = 2-（nicotinoyloxy）acetic acid）, was synthesized using Zn（OAc）2·2H2O and 2-（nicotinoyloxy）acetic acid as raw materials. Its structure has been elucidated by elemental analysis, IR and single-crystal X-ray diffraction. The structural analysis revealed that complex 1 crystallizes in triclinic, space group P1 and the Zn（Ⅱ） atom is six-coordinated with two N atoms from two different 2-（nicotinoyloxy）acetate anion ligands and four O atoms from coordinated water molecules. Complex 1 forms a 3D network structure by O–H···O hydrogen bonds. The antitumor activities of 2-（nicotinoyloxy）acetic acid ligand and its Zn（Ⅱ） complex were evaluated against human lung adenocarcinoma A549 cells, human hepatoma SMMC-7721 cells and human colon carcinoma Wi Dr cells.

Synthesis,Structure and DFT Calculations of a Novel Copper(Ⅱ)Complex Based on Tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate

A novel copper（Ⅱ） complex with tert-butyl 2-[N-（tert-butyloxycarbonylmethyl）-2-picolyamino]acetate（ampy） was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper（II） complex with ampy, [Cu（ampy）Cl2]（1）, was formed irrespective of the metal-to-ligand molar ratios（[Cu2＋]：[ampy] = 0.5：1, 1：1, and 2：1） as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343（2）, b = 18.928（3）, c = 20.058（4） A, V = 4686.1（14） A3, Z = 8, Dc = 1.3349（4） g/cm3, F（000） = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the central copper（II） ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H…Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory（DFT/B3LYP） method with the basis sets（6-31＋G（d,p） for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively）. The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital（NBO） analysis and frontier molecular orbitals（FMOs） analysis were investigated at the same level.

Synthesis,Structure,and Surface Photo-electric Properties of a New Zn(Ⅱ)Coordination Complex Constructed from 2-(1H-benzotriazol-1-yl)acetic Acid and 1,10-Phenanthroline Ligands

A new binuclear Zn^Ⅱ coordination complex,Zn2（bta）（phen）2（Cl）3（1,Hbta = 2-（1Hbenzotriazol-1-yl）acetic acid and phen = 1,10-phenanthroline）,has been synthesized and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental,and photoluminescent analysis.Complex 1 crystallizes in triclinic system,space group P1 with a = 9.3040（19）,b = 10.694（2）,c =16.841（3） A°,α = 101.18（3）,β = 105.77（3）,γ = 91.72（3）°,V= 1575.8（5） A°3,C（32）H（22）Zn2Cl3N7O2,Mr =773.66,Dc = 1.631 g/cm^3,Z = 2,F（000） = 780,μ = 1.820 mm^-1,the final R = 0.1238 and wR =0.1131.X-ray diffraction analyses indicate that 1 displays two crystallographic independent Zn^Ⅱmetal centers with a distorted tetragonal pyramidal（ZnN4O） and a tetrahedral（ZnNCl3） geometries,respectively.The phen serves as a common N,N＇-bidentate ligand,and the bta^- as a unique N,O-bridged ligand in 1.In the crystal,1 forms a stable 3D supramolecular architecture by trifurcated hydrogen bonding C-H…C1 interactions and C-H…π,π…π stacking.1 showed photo-electric conversion properties.

THE EXTRACTED COMPLEX FORMED BY MONO (2-ETHYLHEXYL)-2-ETHYLHEXYL PHOSPHATE WITH DIVALENT Mn

In order to clarify the mechanism and the complex formed in the extraction of divalent Mn by alkylphosphonic acid monoester, the solid complex has been prepared by mono (2-ethylhexyl)-2-ethylhexyl phosphate, HEH(EH)P, HA with divalent Mn. The elemental analysis, magnetic susceptibility and thermogravimetry have been determined for the solid complex of HEH(EH)P-Mn(II) and the infrared spectrum has been carried out in comparison to the extractant HEH(EH)P. The extracted compound has also been studied by electronic and electron spin resonance spectroscopy in octane solvent and solid state at room temperature. On the basis of the measurements, it is concluded that the structure of the solid polymeric species MnA_2 is in a tetrahedral arrangement.

Synthesis, Characterization, Crystal Structure and Antibacterial Activities of a Nickel(Ⅱ) Complex with 2'-(2-Thienylidene)-hydroxybenzoylhydrazide

In the ethanol solvent, a nickel（Ⅱ） complex Ni（C12H10N2O2S）2 upon reaction of 2＇-（2-thienylidene）-hydroxybenzoylhydrazide with nickel acetate was synthesized, and its structure was characterized by IR, UV, elemental analysis and X-ray diffraction analysis. The crystal belongs to monoclinic system, space group C2/c with a = 22.052（3）, b = 5.9681（6）, c = 18.522（2）A , β = 110.679（4）°, V = 2280.6（4）A^3, Z = 4, Mr = 551.27, μ = 1.606 mm^-1, Dc = 1.075 g/cm^3, F（000） = 1136 and Rint = 0.0556. The nickel（Ⅱ ） atom in the compound is four-coordinated with two nitrogen atoms from amide and two oxygen atoms from keto group. The biological activities have been measured, show- ing the compound exhibits better anti-bacterial activity than the ligand.

Synthesis and Crystal Structure of a Ni(Ⅱ) Complex of 2'-[4-N,N'-(Dimethylaminobenzyl- idene)]-3,5-dihydroxybenzoylhydrazide and Its Spectral Properties

A new nickel（II） complex [NiL2]（DMF）4 （HL = 2＇-[4-N,N＇-（dimethylamino- benzylidene）]-3,5-dihydroxybenzoylhydrazide） has been synthesized and its structure was characterized by IR,UV-Vis,1H NMR and elemental analysis. The fluorescence emission mechanism of the complex was discussed by fluorimetric spectra. The single-crystal structure was determined by X-ray diffraction analysis. The crystal belongs to the triclinic system,space group P1 with a = 0.9918（4）,b = 1.1297（4）,c = 1.1331（4） nm,α = 76.860（7）,β = 75.105（6）,γ = 89.022（7）°,V = 1.1936（8） nm^3,Z = 1,μ = 0.472 mm^-1,Dc = 1.319 g/cm^3,F（000） = 502 and Rint = 0.0913. In the title compound,the nickel（II） atom is four-coordinated with two nitrogen atoms from amide and two oxygen atoms from keto group. The complex is centrosymmetric with nickel located at the center.

Synthesis, Characterization of Mn2＊, Co2＊, Ni2＊, Cu2＊ and Zn2. Complex Salts with 2,3,5-（Triphenyl） Tetrazolium Chloride and the Crystal Structure of [C N4（ C6H5）3]2[C uC 14]

A series of new complex salts of the type [R]2[MC14] where R =[Ph-C=n-N-Ph N=N-Ph],M = Mn2＋, Co2＋, Ni2＋, Cu2＋ and Zn2＋ wereprepared and characterized by elemental analysis, molar conductance, IR and UVNis is spectral studies and magnetic measurements.The crystal structure of[Ph-C=n-N-Ph N=N-Ph]2[CuCl4] was determined by single crystal X-ray crystallography. The structure consisted of anion part and a 2,3,5-（triphenyl） tetrazolium cation as counter ions. The copper complex has a distorted tetrahedral geometry, the CI（1）-Cu-CI（2） [124.33 （2°）] and Cl（3）-Cu-Cl（4） [131.03 （2°）] angles are significantly larger than the ideal tetrahedral. The [CuCI4] anion and its counter ions are connected through a hydrogen bonds between C1 of the dianion and hetero aromatic rings by Cl-π, π-π and C-H … π, interactions.