Hydrothermal Synthesis,Crystal Structure and Properties of a New Copper(Ⅱ) Coordination Polymer with 3-(2-Pyridiyl)-1H-1,2,4-triazole(Hpt)

A new copper(Ⅱ) coordination polymer [Cu_2(C_7H_5N_4)_2(3-C_6H_5NO_2)_2]_n(1) has been hydrothermally synthesized with copper hydroxide, 3-(pyridin-2-yl)-1,2,4-triazole(Hpt) and 3-pyridinecarboxylic acid(3-PCA). It crystallizes in the monoclinic space group C2/c, with a=16.854(2), b=7.8616(8), c=20.630(2) ?, β=111.126(2)o, V=2549.7(5) ?3, Dc=1.723 g/cm3, Z=8, F(000)=1336, the final GOOF=1.065, R=0.0380 and w R=0.0972. The whole molecule consisting of two copper ions are bridged by two μ_2-η~1:η~0-3-(pyridin-2-yl)-1,2,4-triazole anions. The coordination environment of Cu(1) ion is CuO_2N_4, giving a distorted octahedron geometry. 1 exhibits antiferromagnetic interaction, and the electron transfer of 1 is irreversible in electrode reactions and the TG analysis shows that 1 is stable below 235 ℃.     

Hydrothermal Synthesis,Crystal Structure and Properties of a 1D Chain Copper(Ⅱ) Polymer with 3-(2-Pyridiyl)-1H-1,2,4-triazole(Hpt)

A new 1D copper(Ⅱ) polymer [Cu(Hpt)(3,5-DMBA)]n has been hydrothermally synthesized with copper acetate,3-(pyridin-2-yl)-1,2,4-triazole(Hpt) and 3,5-dimethylbenzoic acid(3,5-DMBA). It crystallizes in triclinic space group P1,with a = 8.1974(6),b = 8.3280(6),c = 12.5021(9) ?,α = 84.3320(10),β = 71.8870(10),γ= 65.4560(10)o,V = 737.44(9) ?~3,Dc = 1.612 g/cm3,Z = 2,F(000) = 366,GOOF = 1.035,R = 0.0298 and w R = 0.0855. The crystal structure is a one-dimensional(1-D) chain in which the Cu(Ⅱ) is five-coordinated with square pyramidal geometry. The crystal structure shows that the whole molecule consists of two copper ions bridged by two μ12-η:η0-3,5-dimethylbenzoic acid anions and two 3-(pyridin-2-yl)-1,2,4-triazole molecules. The coordination environment of Cu(Ⅱ) ion is CuO+2N_3. The luminescence and thermal properties of the complex were investigated.     

Synthesis,Crystal Structure and Properties of a New Binuclear Copper(Ⅱ) Complex with 5-Oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic Acid(TNCA)

A new binuclear copper(Ⅱ) complex [Cu_2(Hpt)_2(TNCA)_2(H_2O)_2]·4 H_2O(1) has been synthesized with copper acetate, 5-oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic acid(TNCA) and 3-(pyridin-2-yl)-1,2,4-triazole(Hpt). It crystallizes in the triclinic space group P~-_1, with a = 8.8199(18), b = 14.278(3), c = 15.269(3) ?, α = 76.21(3)o, β = 81.07(3)o, γ = 76.07(3)o, V = 1802.7(6) ?~3, Dc = 1.636 g/cm~3, Z = 2, F(000) = 916, the final GOOF = 1.051, R = 0.0556 and wR = 0.1388. The whole molecule consists of two copper ions bridged by two μ_2-η~1:η~0-3-(pyridin-2-yl)-1,2,4-triazole anions. The coordination environment of the Cu(1) ion is CuO_2N_3, giving a distorted square pyramidal geometry. 1 exhibits antiferromagnetic interaction between Cu(Ⅱ) ions, the electron transfer of 1 is irreversible in electrode reactions and the TG analysis shows that 1 is stable below 440 K.     

Hydrothermal Synthesis,Crystal Structure and Properties of a New Binuclear Nickel(Ⅲ) Complex with 3-(Pyridin-2-yl)-1,2,4-triazole

A new binuclear nickel(II) complex Ni₂(HPT)_4(H₂O)₃ (1) has been hydrothermally synthesized with nickel hydroxide,3,4-pyridine dicarboxylic acid and 3-(pyridin-2-yl)-1,2,4-triazole (HPT) in the mixed solution (the volume ratio of methanol and water is 1:4).It crystallizes in tetragonal space group P4₂/n,with a=20.844(1),b=20.844(1),c=7.2463(7)A,V=3148.2(5)A³,D_c=1.587 g/cm³,Z=4,μ(Mo Ka)=1.257,F(000)=1544,the final GOOF=1.043,R=0.0437 and w R=0.1297.The crystal structure shows that the whole molecule consists of two nickel ions which are bridged by fourμ₂-η¹:η^0-3-(pyridin-2-yl)-1,2,4-triazole anions.The coordination environment of Ni(II) ion is Ni N₆,giving a distorted octahedral geometry.The thermal stability and fluorescent and magnetic properties of the complex were investigated.     

Solvothermal Synthesis,Crystal Structure and Characterization of a New Binuclear Nickel(Ⅱ)Complex with 2-(4-Methylbenzoyl)benzoic Acid

A new binuclear nickel(Ⅱ) complex[Ni_2(MBBA)_2(HPT)_2(H_2O)_2]·2H_2O (1) was synthesized with nickel hydroxide,2-(4-methylbenzoyl)benzoic acid (HMBBA) and 3-(pyridin-2-yl)-1H-1,2,4-triazole (HPT).It crystallizes in the monoclinic space group P2_1/n with a=14.5902(13),b=8.8191(6),c=17.6120(14)?,β=110.830(9)o,V=2118.0(3)?~3,M_r=958.26,D_c=1.503 g/cm~3,Z=2,μ(Mo Ka)=0.959,F(000)=992,the final GOOF=1.001,R=0.0353 and w R=0.09864.Each central Ni(II) ion is coordinated by two oxygen and three nitrogen atoms,forming a distorted square pyramidal geometry.The XRD,TG,spectrum analysis and magnetic properties of 1 were studied.     

Solvothermal Synthesis,Crystal Structure and Characterization of a New Binuclear Copper(Ⅱ) Complex with K~3:N~1:N~2:N~4-3-(Pyridin-2-yl)-1,2,4-triazole(HPT)

A new binuclear copper(Ⅱ) complex[Cu_2(MBBA)_2(HPT)_2(H_2O)_2]·2H_2O (1) was synthesized with copper acetate,2-(4-methylbenzoyl) benzoic acid (MBBA) and 3-(pyridin-2-yl)-1H-1,2,4-triazole (HPT).It crystallizes in the monoclinic space group P2_1/c with a=14.722(2),b=8.8907(12),c=18.5565(18)?,β=116.820(7)o,V=2167.6(5)?~3,M_r=483.96,D_c=1.483 g/cm~3,Z=4,μ(Mo Ka)=1.049 mm~(-1),F(000)=981,the final GOOF=0.952,R=0.0586 and w R=0.0823.The whole molecule consists of two copper ions bridged by two HPT molecules.The central Cu(Ⅱ) ion is coordinated by six atoms to give a distorted octahedral coordination geometry.The structure of 1 has been determined by X-ray diffraction,IR spectrum and thermal stability analysis.The solid-state fluorescence displays an obvious emission band at 412 nm upon excitation at 330 nm.Magnetic properties indicate that 1 exhibits antiferromagnetic properties.     

Hydrothermal Synthesis, Crystal Structure, Spectrum and Electrochemical Analysis of the Copper（Ⅱ） Coordination Polymer

The three-dimensional framework copper(Ⅱ) coordination polymer with basic copper carbonate and 3-(pyridin-2-yl)-1,2,4-triazole has been hydrothermally synthesized. It crystallizes in monoclinic space group P21/c, with a = 1.20860(3), b = 1.29581(2), c = 1.67863(3) nm, β = 116.0280(2)°, C21H12Cu3N12, Mr = 623.05, V = 2.36230(9) nm3, Dc = 1.752 g/cm3, Z = 4, F(000) = 1236, GOOF = 1.037, the final R = 0.0408 and wR = 0.1141. Every unit cell contains three copper atoms and three 3-(pyridin-2-yl)-1,2,4-triazole ligands. Every central Cu(Ⅱ) ion is coordinated by four nitrogen atoms of the 3-(pyridin-2-yl)-1,2,4-triazole ligands, forming a distorted tetrahedron. The title complex exhibits an intense photoluminescence at room temperature with the maximum emission at 392 nm. The cyclic voltametric behavior of the complex shows that the electron transfer in electrolysis reaction is irreversible.     

Synthesis,Structure and Norbornene Polymerization Activity of a Novel Palladium(Ⅱ) Complex with N,OBis{1-[[(3-methyl-pyridin-2-yl)amino]methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol} Ligand

The title complex bis{1-[[(3-methyl-pyridin-2-yl) amino] methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol} palladium(C_(42)H_(56)O_2N_4Pd) has been synthesized by the reaction of 1-[[(3-methyl-pyridin-2-yl)amino]methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol with Pd(OAc)_2, and was characterized by IR and elemental analyses(C, H, N). Single-crystal X-ray diffraction analysis of the complex revealed an almost parallelogram geometry of the metal center, space group P1 with a = 12.3870(13), b = 12.9673(12), c = 14.3998(4) ?, α = 67.53(2), β = 75.34(2), γ = 86.89(3)°, V = 2065.5(3) ?~3, M_r = 773.32, Z = 2, D_c = 1.243 g/cm~3, μ = 0.489 mm~(-1), F(000) = 816, the final R = 0.0649 and wR = 0.1567. The compound was investigated for the catalytic behavior towards norbornene(NB) vinyl addition polymerization. And the complex exhibits high catalytic activities up to 1.668 × 10~7 g of PNB(mol of Pd)~(-1) h~(-1) with high monomer conversion using methylaluminoxane(MAO) as the cocatalyst.     

Synthesis and Fluorescent,Magnetic and Thermal Stability Properties of a New Europium(Ⅲ) Complex Eu_2(C_(15)H_(11)O_3)_6(C_(12)H_8N_2)_2

A new europium(Ⅲ) complex Eu_2(C_(15)H_(11)O_3)_6(C_(12)H_8N_2)_2 has been synthesized with 2-(4-Methylbenzoyl)benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: monoclinic, space group P21/n, a = 15.1238(5), b = 13.5928(4), c = 22.9840(7) ?, β = 104.132(3)o, V = 4582.0(2) ?~3, D_c = 1.522 g/cm~3, Z = 4, μ(Mo Kα) = 1.433 mm~(-1), F(000) = 2128, the final R = 0.0447 and wR = 0.0826. The Eu(Ⅲ) ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry. The complex shows two intense fluorescence emission bands arising from the transitions of Eu3+: 5 D0 → 7 F1(594 nm) and 5 D0 → 7 F2(617 nm). The complex is an antiferromagnetism system in the range of 150～300 K. Also reported in the paper is the thermal stability property of the title complex.     

Synthesis and the Fluorescent,Magnetic and Thermal Stability Properties of a New Terbium(Ⅲ) Complex Tb(C_(20)H_(14)O_3N)_3(C_(12)H_8N_2)(H_2O)·H_2O

A new terbium(Ⅲ complex Tb(C_(20)H_(14)O_3N)_3(C_(12)H_8N_2)(H_2O)·H_2O has been synthesized with 2-diphenylanine carbonyl benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: triclinic, space group P1, a =11.6034(6), b = 16.2465(8), c = 16.4427(8) ?, α = 73.168(5)o, β = 88.655(4)o, γ = 82.865(4)o, V = 2943.7(3) ?~3, Dc = 1.494 g/cm~3, Z = 2, μ(MoK α) = 1.272 mm~(-1), F(000) = 1348, the final R = 0.0535 and w R = 0.0809. The Tb(Ⅲ) ion is coordinated by nine atoms to give a monocapped square antiprism coordination geometry. The complex shows four fluorescence emission bands arising from the transitions of Tb~(3+): ~5D_4 → ~7F_6(491 nm), ~5D_4 → ~7F_5(546 nm), ~5D_4 → ~7F_4(585 nm) and ~5D_4→~7F_3(621 nm). Also reported are the magnetic and thermal stability properties of the complex.     

Crystal Structure,Spectroscopic Characterization,and Electrochemical and Thermal Stability Properties of a Dinuclear Nickel(Ⅱ) Complex

A new nickel(Ⅱ) complex Ni_2(L)_2(2,2?-bipy)2·5.5H_2 O with methy-bicycle[2.2.1]hept-5-ene-2,3-dicarboxylic acid(H2L) and 2,2?-bipyridine(2,2?-bipy) as ligands has been synthesized in the mixed solvent DMF and water(v:v = 5:2). It crystallizes in the triclinic space group P1 with a = 10.414(2), b = 12.884(3), c = 16.176(4) ?, α = 70.715(5), β = 80.599(5), γ = 77.383(6)o, V = 1989.4(8) ?3, Dc = 1.531 g/cm3, Z = 2, F(000) = 958, GOOF = 1.028, the final R = 0.0808 and w R = 0.2036. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two nickel ions are bridged by two μ2-η1:η0 3-carboxylate groups of L2- anions. The coordination environment of Ni(Ⅱ) ion is Ni N_2O_3, giving a distorted square pyramidal geometry. The thermal stability and electrochemical properties of the complex were investigated.     

Synthesis, Crystal Structure and Photoluminescent Property of a Novel Disilver Complex with Pyrazinyl Oxime Ligand

<正>A novel binuclear Ag(I) complex [Ag_2(C_6H_6N_3O)_2(C_6H_7N_3O)_2]·2CH_3CN (1) was synthesized by the evaporation reaction of silver nitrate and (E)-1-(pyrazin-2-yl)ethanone oxime (HL). The complex was characterized by elemental analysis, IR spectrum and X-ray single-crystal diffraction analysis. It crystallizes in the monoclinic space group C2/c with a = 22.7089(3), b = 11.5443(7), c = 16.1468(4) , β = 127.7150(10)°, V = 3348.6(2) ~3, D_c = 1.675 g/cm~3, M_r = 844.42, Z = 4, F(000) = 1696.0, μ = 1.226 mm~(-1), the final R =0.0250 and wR = 0.070. The coordination around the silver(I) atom is a distorted trigonal-bipyramidal geometry involving one protonated pyrazinyl oxime ligand (HL), one deprotonated oxime ligand (L~-) and one CH_3CN solvate molecule in the asymmetric unit of complex 1.     

Syntheses,Structures and Characterizations of Two New Zinc(Ⅱ) Coordination Polymers Constructed from 3-(1H-Pyrazol-4-yl)-5-(pyridin-2-yl)-1,2,4-triazole and Different Carboxylate Ligands

Two new zinc(Ⅱ) coordination polymers, [Zn(ph)(H2 L)·H_2O]2 n(1) and [Zn(ip)(H2 L)-(H_2O)]n(2)(H2 ph = phthalic acid, H2 ip = isophthalic acid, H2L = 3-(1 H-pyrazol-4-yl)-5-(pyridin-2-yl)-1,2,4-triazole), have been successfully synthesized via hydrothermal reaction. It has been structurally characterized by X-ray single-crystal analysis, IR spectra, fluorescence spectroscopy and thermogravimetry analysis. The single-crystal X-ray diffraction studies reveal that compounds 1 and 2 both exhibit 1D chain structures, and assemble into 2D and 3D supermolecules through hydrogen bonds or π-π interactions. Moreover, the thermal stability and luminescent properties of compounds 1 and 2 were also studied.     

Aromatic Multicarboxylate Ligands Tuned One-and Three-dimensional Zn(Ⅱ) Coordination Polymers Based on 3-(1H-pyrazol-4-yl)-5-(pyridin-3-yl)-1,2,4-triazole

Two aromatic multicarboxylate ligands tuned Zn(Ⅱ) coordination polymers, namely, {[Zn_(0.5)(H_2L)(tp)_(0.5)(H_2O)]H_2O}_n(1) and {[Zn_2(HL)(btc)(H_2O)]H_2O}_n(2)(H_2L = 3-(1 Hpyrazol-4-yl)-5-(pyridin-3-yl)-1,2,4-triazole, H_2tp = terephthalic acid; H_3 btc = 1,3,5-benzenetricarboxylic) have been synthesized. Their structures were characterized by single-crystal X-ray diffraction analysis, elemental analyses and infrared spectra. Compound 1 possesses a one-dimensional chain structure and is finally extended into a three-dimensional supramolecular architecture though hydrogen bonding interactions. Compound 2 shows a three-dimensional framework. Meanwhile, compounds 1 and 2 exhibit luminescent emission in the solid, and can be investigated as potential luminescent materials.     

A New Cd(Ⅱ) Coordination Compound Based on 4-(1,2,4-Triazol-4-yl)phenylacetic Acid:Synthesis,Structure and Photoluminescence Property

A new complex [Cd_2(L)_2(Cl)_2(H_2O)]_n(1) was synthesized by reacting CdCl_2·2.5 H_2O with 4-(1,2,4-triazol-4-yl)phenylacetic acid(HL) ligand.The structure of the complex was characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental analysis and PXRD.Complex 1 crystallizes in triclinic,space group P21/c with a = 11.4303(8),b = 14.1792(10),c = 14.6857(10) ?,β = 96.3780(10)o,V = 2365.4(3) ?~3,Z = 4,C_(20)H_(16)Cl_2N_6O_5Cd_2,M_r = 716.09,D_c = 2.011 g/cm3,μ = 2.069 mm~(-1),S = 1.051,F(000) = 1392,the final R = 0.0458 and wR = 0.0949 for 5402 observed reflections(I 2σ(I)).Complex 1 is a two-dimensional(2D) layer structure and non-covalent bonding interactions such as C–H···π and π···π extend the 2D to form a three-dimensional supramolecular polymer.     

A Novel Phenoxyimine-based Schiff Base Ligand and Its Mononuclear Nickel(Ⅱ) Complex:Synthesis,Crystal Structure,Norbornene Polymerization and Catalytic Activity

A novel phenoxyimine-based Schiff base ligand and its mononuclear complex [C_(58)H_(52)N_2NiO_2](L = 2-benzhydryl-4-dimethoxy-3,5-dimethyl-salicylaldehyde) has been synthesized and characterized by IR spectrum, elemental analysis, TG, WAXD spectra, ~1H NMR and ~(13)C NMR. In addition, the molecular structure has been measured by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P2_1/c with a = 14.510(6), b = 18.573(7), c = 20.961(6) ?, β = 123.453(19)°, V = 4713(3) ?~3, M_r = 867.73, Z = 4, D_c = 1.223 g/cm~3, μ = 0.456 mm~(-1), F(000) = 1832, the final R = 0.0685 and wR = 0.1758(I 2σ(I)). The complex was used as homogeneous catalysis of polymerization of norbornene, and the MAO as cocatalyst. The nickel complex exhibited good catalytic activity up to 1.913 × 10~7 g of PNB(mol of Ni)~(-1)h~(-1),and the yields of these reactions depend on the nature of the substituent in the aromatic ring.     

Hydrothermal Synthesis,Crystal Structure,Spectrum Properties and Quantum Chemical Calculation of a Trinuclear Copper（Ⅱ） Complex with 3-（Pyridin-2-yl）-1,2,4-triazole

A three-dimensional framework copper(Ⅱ) coordination polymer with copper carbonate basic and 3-(pyridin-2-yl)-1,2,4-triazole (Hpt) has been hydrothemally synthesized.The complex (2,C14 H10 CuN8 ·3H2 O) crystallizes in tetragonal,space group P4 2 /n,a=2.08581(12),b=2.08581(12),c=0.72331(4) nm,M r=761.73,V=3.1468(3) nm 3,Dc=1.608 g/cm 3,Z=4,F(000)=1552,GOOF=1.07,R=0.0515 and wR=0.1689.Every asymmetric unit molecular structure of the complex is composed with one copper ion,one and half water molecules and two Hpt molecules.Each copper ion is coordinated with five nitrogen atoms from four Hpt molecules,forming a distorted square pyramidal geometry.The fluorescence spectrum analysis shows that the title complex at room temperature exhibits intense photoluminescence with maximum emission at 450 nm.The quantum chemistry calculation study on the complex has been performed.The stability,some frontier molecular orbital energies and composition characteristics of some frontier molecular orbitals of the complex have been investigated.     

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Binuclear Copper（Ⅱ） Complex with 3-（Pyridin-2-yl）-1,2,4-triazole

One novel binuclear copper(Ⅱ) complex [Cu 2 (Hpt) 2 (CO 3) 2 (H 2 O) 2 ]·H 2 O with copper carbonate and 3-(pyridin-2-yl)-1,2,4-triazole (Hpt) was hydrothermally synthesized and characterized by IR and X-ray diffraction analysis.The complex crystallizes in triclinic,space group P2 1 /n with a=0.6862(1),b=0.7805(1),c=1.1983(2) nm,α=72.03(2),β=107.72(3),γ=75.28(2)o,V=0.5884 nm 3,D c=2.105 g/cm 3,Z=1,F(000)=357,GOOF=1.041,the final R=0.01859 and wR=0.04348.The whole molecule is composed of two cooper ions,two Hpt molecules,two carbonate and three water molecules,forming a binuclear structure.The crystal structure shows that the cooper ion is coordinated with three nitrogen atoms from two Hpt molecules,two oxygen atoms from one carbonic acid and one water molecule,forming a distorted square pyramidal geometry.The TG analysis result shows that the title complex is stable under 131.0 ℃.     

Synthesis,Fluorescence and Magnetic Properties of a New Europium(Ⅲ) Complex Eu(C_(14)H_9O_3)_2(C_(12)H_8N_2)_2(NO_3)

A new europium(III)complex Eu(C_(14)H_9O_3)_2(C_(12)H_8N_2)_2(NO_3)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2_1/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D_c=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm~(-1),F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu~(3+):~5D_0→~7F_1(594 nm)and ~5D_0→~7F_2(618 nm).In addition,its X_(m )T decreases from 1.29767 cm~3?mol~(-1)?K at 300 K to 0.01531 cm~3?mol~(-1)?K at 2 K.     

Synthesis,Structure and Norbornene Polymerization Catalyzed by Bis{(2-benzhydryl-4,6-dimethyl-phenyl)-(3,5-di-tert-butyl-2-methyl-benzylidene)-amine-N,O}nickel(Ⅱ)

The title complex bis{(2-benzhydryl-4,6-dimethyl-phenyl)-(3,5-di-tert-butyl-2-methyl-benzylidene)-amine-N,O}nickel has been synthesized by the reaction of(2-benzhydryl-4,6-dimethyl-phenyl)-(3,5-di-tert-butyl-2-methyl-benzylidene)-amine with Ni(CH_3COO)_2·4H_2O, and characterized by IR spectrum and single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P2_1/c with a = 12.373(4), b = 18.434(7), c = 27.814(10) ?, β = 92.291(6)o, V = 6339(4) ?~3, C7 2H8 0N2 Ni O_2, M_r = 1064.09, Z = 4, D_c = 1.115 g/cm~3, μ = 0.350 mm~(-1), F(000) = 2280, the final R = 0.0846 and wR = 0.2926(I 2s(I)). This title compound was used as homogeneous catalysis of polymerization of norbornene, and the complex exhibited good catalytic activity to catalyze norbornene polymerization using MAO as a cocatalyst.