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.

A One-dimensional Cd(Ⅱ)Coordination Polymer Constructed from 1,4-Benzene-dicarboxylic Acid and 3-(2,6-Di(pyrazin-2-yl)pyridin-4-yl)-1H-indole:Synthesis,Structure and Photoluminescence

A new coordination polymer {[Cd（C_（21）H_（14）N_6）（C_8H_4O_4）]·H_2O}_n（1） was synthesized by an elaborate design via the reaction of 3-（2,6-di（pyrazin-2-yl）pyridin-4-yl）-1H-indole（bppi）,1,4-benzene-dicarboxylic acid（H2bdc） and cadmium（Ⅱ） nitrate in CH_3OH/H_2O mixed solvents. Complex 1 crystallizes in orthorhombic,space group Ccca with a = 20.012（4）,b = 31.881（6）,c = 19.808（4） ？,V = 12638（4） ？~3,Z = 16,C_（29）H_（20）CdN_6O_5,M_r = 644.91,D_c = 1.356 g·cm^（-3）,μ = 0.735 mm^（-1）,F（000） = 5184,GOOF = 1.046,the final R = 0.0405 and wR = 0.1063 for 6870 observed reflections（I 〉 2σ（I））. The Cd（Ⅱ） centre is hepta-coordinated by three N and four O atoms from one bppi terminal ligand and two bdc2– ligands,respectively,displaying a capped trigonal prism geometry. Structure extension gives coordination polymeric chains,in which the bdc2– linkers connect Cd（Ⅱ） cations into a one-dimensional（1D） coordination polymer along the c axis,giving zigzag chains with the Cd···Cd separation of 11.178（1） ？. The adjacent bppi terminal ligands in the chains are anti-periplanar conformation. The three-dimensional（3D） structure is stabilized by π···π stacking and hydrogen-bonding interactions to form a supramolecular self-penetrating network with 1D channels. In 1,there are voids 2999.7 ？~3 with 23.7% of per unit cell volume. Thermal analysis indicates that the framework of 1 is stable until 651 K and the photoluminescence of 1 in the solid shows very weak fluorescence at 382 and 560 nm upon excitation at 310 nm.

Synthesis,Crystal Structure and Properties of a Zinc(Ⅱ) Complex Based on 5-(1H-Tetrazol-5-yl)isophthalic Acid Ligand

A novel polymeric zinc（II） complex {[Zn2（TIA）（H2O）3]·（NO3）}n（1, H3TIA = 5-（1H-tetrazol-5-yl）isophthalic acid） has been synthesized in mixed solvents under solvothermal conditions and characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 crystallizes in orthorhombic, space group Cmcm with a = 10.4210（6）, b =23.3526（14）, c = 6.9214（4）A, V = 1684.37（17）A^3, Z = 4, C9H4N5O（10）Zn2, Mr = 472.91, Dc = 1.865g/cm^3, F（000） = 932, λ（MoK α） = 2.909 mm^-1, R = 0.0423 and wR = 0.1287. The complex has good thermal stability and excellent photoluminescent property.

Metal-organic frameworks derived from divalent metals and 4-(1H-1, 2, 4-triazol-1-yl)benzoic acid

Two inorganic-organic coordination polymers, [Cd(TBA)2]·3H2O (1) and [Cu(TBA)2]·2H2O (2) have been synthesized by reaction of the metal ions of Cd(II) and Cu(II) with the ligand HTBA [HTBA = 4- (1H-1, 2, 4-triazol-1-yl)benzoic acid] under solvothermal condition. The compounds were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, X-ray powder diffraction (XRPD), and thermo gravimetric analysis (TGA). The structural analyses reveal the two independent polymers exhibit different structures. Complex 1 exhibits a 3D framework with 1D channels, and complex 2 shows a 2-fold interpenetrating 3D diamond net.

A Y(Ⅲ)-organic Coordination Polymer Constructed from 2-(Pyridine-4-yl)-1H-imidazole-4,5-dicarboxylate and Oxalate Ligands: Structure and Luminescent Property

A novel compound, {[Y（HPIDC）（OX）1/2（H2O）]·2H2O}n （1, H3PIDC = 2-（pyridin-4- yl）-1H-imidazole-4,5-dicarboxylic acid, H2OX = oxalic acid）, has been synthesized under hydrothermal conditions and characterized by thermal analysis （TGA）, powder X-ray diffraction （PXRD）, and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic space group P21/c with a = 8.342（8）, b = 14.61（1）, c = 11.487（1）, β = 90.78（9）°, V = 1400.4（2）3, Z = 4, C11H11N3O9Y, Mr = 418.14, Dc = 1.983 g/cm3, F（000） = 836, Rint = 0.0509, T = 293（2） K, μ = 4.240 mm-1, the final R = 0.0477 and wR = 0.1125 for 2770 observed reflections with I 2σ（I）. Compound 1 exhibits a 3D framework and generates the 1D open channels filled with free water molecules. The structure of 1 can be rationalized as a diamondoid network when the atom yttrium is regarded as a 4-connected node linking four surrounding yttrium atoms. The luminescent property of compound 1 is also investigated.

Hydrothermal Synthesis and Crystal Structure of One Novel 1-D Copper(Ⅱ)-organic Framework:{[Cu_2(PP)_2(CBPC)]_2·7H_2O}_n

One novel 1-D copper（Ⅱ）-organic compound,namely {[Cu2（PP）2（CBPC）]2·7H2O}n（1,H2CBPC=1-[（2＇-carboxybiphenyl-4-yl）methyl]-2-propylimidazole-4-carboxylic acid,HPP=3-（2-pyridyl）pyrazole）,was synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that the two Cu（Ⅱ） ions in the distorted dimer [Cu2（PP）2] of 1 are linked by the carboxylate oxygen atoms on the phenyl and imidazole rings,respectively,forming one interesting snake-like chain.Single-crystal X-ray analyses reveal that it crystallizes in monoclinic,space group C2/c with a=30.656（8）,b=12.715（3）,c=22.405（5）,β=122.758（3）°,V=7344（3）3,Z=4,Mr=1681.65,Dc=1.521 g/cm3,F（000）=3464,μ=1.221 mm-1,the final R=0.0453 and wR=0.1023 for 4617 observed reflections with Ⅰ 〉2σ（Ⅰ）.

Improvement in the synthesis of 2-(5-amino-1,2,4-thiadiazol-3- yl)-2-(Z)-methoxyiminoacetic acid 2-benzothiazolyl thioester

2-(5-Amino-1,2,4-thiadiazol-3-yl)-2-(Z)-meth-oxyiminoacetic acid 2-benzothiazolyl thioester(III),an important intermediate of the fourth generation cephalos-porins,was efficiently synthesized by reacting 2-(5-amino-1,2,4-thiadiazol-3-yl)-2-(Z)-methoxyiminoacetic acid(I)with 2,29-dibenzothiazole disulfide(II)in the presence of triphenylphosphine.Effects of reaction time,temperature,solvents,catalysts and feeding molar ratio on the yield and quality of products were investigated,and an im-proved procedure suitable for industrial production was established.Using 1,2-dichloroethane as solvent,triphe-nylphosphine as reducer,and triethylamine as catalyst,n(I):n(II):n(triphenylphosphine)51.0:1.0:1.0,the product was obtained at room temperature in 98.1%yield.The purity of the product without further purification is 98.7%determined by HPLC method.This procedure could be a suitable alternative to the traditional processes because of its easy handling,high yield and low cost.

Synthesis of 5-[(2-hydroxynaphthalen-1-yl)diazenyl]isophthalic acid and its application to electrocatalytic oxidation and determination of adrenaline,paracetamol,and tryptophan

In this study,Au nanoparticles/poly 5-[（2-hydroxynaphthalen-l-yl）diazenyl]isophthalic acid film modified glassy carbon electrode（AuNPs/poly（NDI）/GCE） has shown excellent electrocatalytic activity toward the oxidation of adrenaline（ADR）,paracetamol（PAC）,and tryptophan（Trp）.The bare glassy carbon electrode（GCE） fails to separate the oxidation peak potentials of these molecules,while the poly（NDI） film modified electrode can resolve them.Electrochemical impedance spectroscopy（EIS）indicates that the charge transfer resistance of the bare electrode decreases as 5-[（2-hydroxynaphthalen-l-yl）diazenyl]isophthalic acid is electropolymerized on the bare electrode.Furthermore,EIS exhibits enhancement of electron transfer kinetics between analytes and the electrode after electrodeposition of Au nanoparticles.Differential pulse voltammetry results show that the electrocatalytic current increases linearly in the ranges of 0.01-680.0 μmol L^-1 for ADR,0.05-498.0 μmol L^-1 for PAC,and 3.0-632.0 μmol L^-1 for Trp;with detection limits（S/N = 3） of 0.009 μmol L^-1,0.005 μmol L^-1,and 0.09 μmol L^-1 for ADR,PAC,and Trp,respectively.The proposed method has been successfully applied for simultaneous determination of ADR,PAC,and Trp in biological samples.

Synthesis,Structure,and Magnetic Property of One Snake-shaped Copper(Ⅱ)-organic Compound:Cu[Cu_2(PP)_2](CBPC)_2]·2(H_2O)

One novel copper（II）-organic compound,namely Cu[Cu2（PP）2]（CBPC）2]·2（H2O）（1,H2CBPC = 1-[（2＇-carboxybiphenyl-4-yl）methyl]-2-propylimidazole-4-carboxylic acid,HPP = 3-（2-pyridyl）pyrazole）,was designed and synthesized under hydrothermal conditions.X-ray diffraction analysis reveals that two Cu（II）ions in the quasi-planar dimmer of [Cu2（PP）2] are linked by the carboxylate oxygen atoms on the phenyl ring and the imidazole ring,respectively,yielding one snake-shaped structure.Magnetic measurements reveal that compound 1 shows the strongly antiferromagnetic property.Crystal data of 1：C58H52Cu3N10O10,Mr = 1239.72,monoclinic,P21/c,a = 14.900（7）,b = 15.029（7）,c = 12.308（6）,β = 102.519（9）o,V = 2691（2）3,Z = 2,Dc = 1.530 g/cm3,F（000）= 1274,μ = 1.246 mm-1,R = 0.0416,wR = 0.0780（I 2σ（I））and S = 0.999.

Synthesis, Structure and Physical Property of a New 3D Lead Coordination Polymer: [Pb_2(L)_2(dea)]_n·nH_2O

A new 3D Pb（II） coordination polymer [Pb2（L）2（dea）]n-nH20 has been hydrothermally prepared by using the long flexible decanedioic acid （H2dea） and the N-donor chelating ligand 2-（1 H- 1,3,7,8-tetraazacyclopenta[1]phenanthren-2-yl）naphthol （HL）. Single-crystal X-ray determi- nation shows that the complex crystallizes in the monoclinic system, space group C2/c with a = 25.453（5）, b = 7.5035（15）, c = 27.340（6） A, β = 114.84（3）, V = 4738.6（16） A3, Z = 8, C28H22NaOaPb, Mr = 685.69, Dc = 1.922 g/cm3, F（000） = 2656,/u（MoKa） = 7.166 mm-1, R = 0.0282 and wR = 0.0687. Two L ligands bridge two Pb（II） atoms to form a dimmer, and the neighboring dimers are further linked by the dea ligands to yield a 3D structure. The IR and TG of the compound have been investigated in detail.

Fe-catalyzed regioselective Friedel–Crafts hydroxyalkylation of N-substituted glyoxylamide with indoles

An efficient regioselective Friedel-Crafts hydroxyalkylation of N-substituted glyoxylamide with various indoles catalyzed by Lewis acids was developed. The reactions proceeded smoothly at room temperature and the 2-hydroxy-2-（1H-indol-3-yl）-N-substituted acetamide resulted from the reactions catalyzed by FeSO4 were synthesized in excellent yields （up to 93%）. While the bisindole compounds were obtained when FeCl3 was used as a catalyst in excellent yields （up to 92%）. A possible mechanism was proposed.