One Novel Mn(Ⅱ)Complex with 1-Substituted-1H-1,2,3-triazole-4-carboxylic Acid:Crystal Structure,Fluorescence and Hirshfeld Surface Analysis

The crystal structure of one novel Mn（II） complex, [Mn（pmta）_3]_2[Mn（H_2O）_6]·4H_2O（1）, is reported（Hpmta = 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid）. In the title compound, the asymmetric unit consists of a [Mn（pmta_）3]ˉ anion, half [Mn（H_2O）_6]^（2＋） counter cation and two lattice H_2O molecules, and the intra- and intermolecular hydrogen bonds connect the complex into a supramolecular structure. The liquid-state fluorescence spectra of complex 1 have been determined. Hirshfeld surface analysis was also studied. The main intermolecular interactions in the complex are O···H and H···H contacts.

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.

Syntheses and Crystal Structures of Hg(Ⅱ)and Ag(Ⅰ)Complexes Containing 2-Acetylpyridine-paminobenzoylhydrazone Ligand

The two complexes [HgI_2L]（DMF）（1） and [AgL_2]（ClO_4）（CH_3CN）（2） were synthesized from the reaction of Schiff base ligand（2-acetylpyridine-p-aminobenzoylhydrazone）（L） with HgI_2 or AgClO_4 respectively. The compounds are characterized by ^1H NMR,FTIR and elemental analysis. The structures of the ligand and two complexes are measured via single-crystal X-ray diffraction. In these two complexes,the structures are both distorted triangular bipyramids with five-coordinated centers.

Synthesis,Crystal Structure and Optical and Photocatalytic Properties of a Discrete Cuprous Iodide Compound with a Transition Metal Complex Cation

With transition metal complex, a discrete cuprous iodide compound, namely, [Ni（phen）3]2Cu6I10（1, phen = 1,10-phenanthroline） has been solvothermally synthesized and structurally characterized. Single-crystal X-ray diffraction studies revealed that compound 1 crystallizes in triclinic space group P1（No. 2） with a = 11.2694（2）, b = 12.3699（3）, c = 15.0387（3） ？, α = 102.840（2）, β = 105.215（2）, γ = 96.388（2）°, V = 1940.04（7） ^3, Z = 1, Dc = 2.438 g·cm^-3, F（000） = 1324, R = 0.0256 and w R = 0.0555（I 〉 2σ（I））. Compound 1 features a discrete anionic moiety of [Cu6I10]^4- charge-balanced by two metal complexes of [Ni（phen）3]2＋. The optical absorption edge of compound 1 was estimated to be 2.24 eV. Interestingly, nearly 95% of contaminant（crystal violet aqueous solution（CV）, 50 m L, 1.0 × 10^-5 M） could be decolorized after exposure to visible light within 30 min, illustrating an impressive photocatalytic activity of compound 1. The thermal stability of 1 has also been studied.

Synthesis,Crystal Structure and Catalytic Performance of the Trifluoro-substituted Mono(β-diiminato)Copper(Ⅱ)Complex

Two novel copper complexes with methyl or trifluoro-substituted mono-β-diiminato ligands and one acetoxyl anion were synthesized and characterized by IR spectroscopy and elemental analysis for the first time. The structure of complex 2 bearing trifluoro substituents was further confirmed by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 7.377（4）, b = 11.727（6）, c = 12.913（7） ？, α = 116.569（6）, β = 98.829（7）, γ = 96.520（6）°, V = 966.2（8） ？3, Z = 2, Mr = 479.86, Dc = 1.649 g/cm3, F（000） = 482, μ = 1.205 mm-1, the final R = 0.0370 and w R = 0.0903 for 3430 observed reflections with I 〉 2σ（I）. These mono-β-diiminato copper complexes can effectively catalyze methacrylate（MA） polymerization when activated by MMAO. The introduction of fluoro groups into the N-aryl ring of β-diiminato ligands can greatly increase the catalytic activity of copper complexes as well as the molecular weight of PMA.

Syntheses,Crystal Structures and Antibacterial Activities of Schiff Base of Nickel(Ⅱ)and Copper(Ⅱ)Complexes

A new kind of Schiff base HL（HL= 1-phenyl-3-methyl-4-（p-methylbenzoyl）-5-pyrazolone with L-Leucine methyl ester） and complexes Ni L′_2·0.75C_2H_5OH·0.25H_2O,Cu L′′2（L′ = 1-phenyl-3-methyl-4-（p-methylbenzoyl）-5-pyrazolone with L-leucine ethyl,L′′ = 1-phenyl-3-methyl-4-（p-methylbenzoyl）-5-pyrazolone with L-leucine） have been synthesized and structurally determined by X-ray diffraction. For HL： crystal structure determination indicates that there are two independent HLs with different conformations in one asymmetric unit. For complex 1： the Ni（Ⅱ） ion is six-coordinated by two carbonyl oxygen atoms from pyrazolone ring,two nitrogen atoms from different HL′ and two oxygen atoms from L-Leucine ethyl ester to form a distorted octahedral geometry. For complex 2： the Cu（Ⅱ） ion is four-coordinated by one carbonyl oxygen atom from the pyrazolone ring,one nitrogen atom from HL′′,and two different carboxylic oxygen atoms from L-leucine with the same conformation to form a distorted quadrilateral geometry.

Synthesis, Crystal Structure and Fluorescent Property of a Zn(Ⅱ) Complex with 1,3-Bis(imidazol-1-yl)benzene and 1,3-Benzenedicarboxylate

A novel zinc complex [Zn（BIB）（bdc）]n（1, BIB = 1,3-bis（imidazol-1-yl）benzene, bdc = 1,3-benzenedicarboxylate） has been synthesized in solvothermal conditions. The title complex was characterized by elemental analysis, IR spectra, thermal analysis, single-crystal and powder X-ray diffraction. The result proved that the alliance of BIB and aromatic carboxylic acids is good for the diversity of getatable structure. Complex 1 crystallizes in the monoclinic system of P2/c space group with a = 11.5591（10）, b = 9.6239（8）, c = 33.727（3）A, β = 103.816（3）°, V = 3643.4（5） A^3, Z = 8, μ = 1.385 mm^-1, F（000） = 1792, Dc = 1.603 g/cm^3 and Mr = 439.72 g/mol. Additionally, luminescent properties of complex 1 are also investigated and it shows good fluorescence.

Synthesis,Crystal Structure and Photoluminescence of a TADF Cuprous Complex

A cuprous mononuclear copper complex [Cu（adpypz）CH3CNPPh3]BF4·CH2Cl2（1, adpypz = 9,9-dimethyl-10-（6-（3-phenyl-1H-pyrazol-1-yl）pyridin-2-yl）-9,10-dihydroacridine） was synthesized and characterized by Elemental Analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic, space group P1 with a = 11.3388（4）, b = 13.4569（4）, c = 16.2561（6） ？, α = 97.154（3）, β = 92.187（3）, γ = 114.119（4）°, V = 2235.38（13） ？3, Z = 2, Mr = 967.12, Dc = 1.437 g/cm^3, F（000） = 996, μ = 2.62 mm^–1, GOOF = 1.031, the final R = 0.0417, and w R = 0.1024 for 8043 observed reflections with I 〉 2σ（I）. The Cu（I） atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. In the solid state, the complex exhibits bluish-green photoluminescence with emission peaks λmax = 492 nm（1）, lifetimes 235 μs and quantum yields（ф = 0.279） at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that the complex displays thermally activated delayed fluorescence（TADF） at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ILCT excited states.

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）N2NiO2]（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 P21/c with a = 14.510（6）, b = 18.573（7）, c = 20.961（6） A, β = 123.453（19）°, V = 4713（3）A^3, Mr = 867.73, Z = 4, Dc = 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）^-1h^-1,and the yields of these reactions depend on the nature of the substituent in the aromatic ring.

Synthesis,Crystal Structure and Redox Property of a Copper(Ⅱ)Complex Based on 1,1-Bis(1H-benzoimidazol-2-ylmethyl)cyclohexane

A novel mononuclear copper（Ⅱ） complex [Cu（bbmc）Cl_2]·DMF,where bbmc is 1,1-bis（1H-benzoimidazol-2-ylmethyl）cyclohexane,was synthesized and characterized by X-ray single-crystal structure analysis.The complex crystallizes in triclinic,space group P1 with a = 9.1088（5）,b = 11.0075（4）,c = 14.2326（6）A,α = 97.188（3）,β = 96.394（4）,γ = 111.430（4）°,V = 1298.73（10） A^3,Z = 2,D_c = 1.409 g/cm^3,μ（Mo Kα） = 1.074 mm^-1,F（000） = 572,S = 1.078,R = 0.0381 and w R = 0.0876 for 5593 observed reflections with I 〉 2σ（I）.The central Cu（Ⅱ） ion adopts a distorted tetrahedral geometry coordinated by two nitrogen atoms of the ligand and two chloride ions.The complex showed its thermal decomposition temperature up to 226 ℃ and exhibited an irreversible one-electron transfer process involving Cu^Ⅱ/Cu^I couple.

Synthesis,Crystal Structure and Photoluminescence of a Dinuclear Cuprous Complex with Thiocyanate Bridges

A cuprous dinuclear copper complex [PPh_2PAr_2Cu（μ-SCN）_2CuPPh_2PAr_2]（1,PPh_2PAr_2 =（1-bis（2-methylphenyl）-phosphine-2-diphenylphosphino）benzene） was synthesized from the reaction of Cu SCN and PPh_2PAr_2 in CH_3CN at room temperature. The compound was characterized by Elemental Analysis,NMR,UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic,space group P1 with a = 10.225（2）,b = 11.360（2）,c = 13.420（3） ？,α = 95.81（3）,β = 93.45（3）,γ = 113.78（3）°,V = 1410.4（5） ？~3,Z = 1,Mr = 1192.21,Dc = 1.404 g/cm^3,F（000） = 616,μ = 3.029 mm^（–1）,GOOF = 1.052,the final R = 0.0359,and w R = 0.0964 for 4878 observed reflections with I 〉 2σ（I）. The Cu（I） atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. The copper centers in the molecular structure are bridged by two thiocyanate anions and each Cu（I） is chelated further terminally by a PPh_2PAr_2 ligand. The [Cu（μ-SCN）_2Cu] cores have essential planar configurations. In the solid state,the complex exhibits blue photoluminescence with emission peaks λ_（max）= 478 nm（1）,lifetimes 4.7 μs and quantum yields（ф = 0.43） at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that it displays thermally activated delayed fluorescence at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ^（1,3）MLCT excited states.

CRYSTAL STRUCTURE OF A TRINUCLEAR COBALT COMPLEX Co_3(bdt)_3(PBu_3~n)_3 · ~2CH_2C1 (bdt = S_2C_6H_4~2- ) WITH MIXED o-BEN-ZENEDITHIOLATE AND TRIBUTYLPHOSPHINE LIGANDS

Co3(S2C6H4)3{P(C4H9)3}3 ·2CH2Cl2, Mr = 1373. 45, mono-clinic, space group P21/c, a = 16. 110(5), b=36.313(10), c=13. 502(5) A , β= 105. 69(4)% V=7604. 4 A3, Z = 4, Dc = 1. 20 g. cm-3, μ=10. 03 cm-1, and F (000) = 2990. R(Rw) is 0. 086(0. 091) for 4559 observed unique reflections. The three cobalt atoms in the complex form an isosceles triangle with an average Co -Co bond distance of 2. 504(5) A. The average values of Co - S and Co - P bond distances are 2. 271(7) A , and 2. 198(8) A , respectively.

Thiocyanate-controlled Copper(Ⅱ)-L-arginine Complex:Synthesis,Crystal Structure and Characterization

A novel thiocyanate-controlled copper（Ⅱ）-L-arginine complex with the formula of Cu（Arg）（SCN）2（1,Arg：L-arginine） has been obtained from aqueous solution and structurally characterized by single-crystal X-ray diffraction method.Crystal data：orthorhombic,space group P212121,a = 6.0156（5）,b = 12.1905（11）,c = 18.4203（16） A°,V = 1350.8（2） A°3,Z = 4,μ = 1.933mm^（-1）,F（000） = 724,S = 1.084,the final R = 0.0410,wR = 0.0754 for 1893 observed reflections with I 〉 2σ（I）,and R = 0.0559,wR = 0.0820 for all reflections.In addition,elemental analysis,IR,TG-DTG and magnetism characterization are presented.

Synthesis, Crystal Structure and Luminescence Property of a Cd(Ⅱ) Complex Assembled by 4-Carboxymethoxy Phenylacetic Acid

A new structure with the molecular formula [CdL]n was formed by CdSO4 with 4-carboxymethoxy phenylacetic acid （H2L） through the hydrothermal method. The complex was characterized by elemental analysis and infrared spectroscopy. The structure of the complex was determined by single-crystal X-ray diffraction, which is of monoclinic system, space group P21/c with a = 10.3887（2）, b = 7.10710（10）, c = 14.7212（2） , β = 120.6940（10）°, V = 934.65（3） 3, Dc = 2.278 g·cm-3, Z = 4, F（000） = 624, S = 1.022, the final R = 0.0187 and wR = 0.0487 for 2000 observer reflections （Ⅰ 〉 2σ（Ⅰ））. The center metal ion Cd（Ⅱ） in the complex is six-coordinated in a distorted octahedral geometry, and is connected with L ligands to form a 3D fishing net structure, which is a novel （3,6） network topology. The luminescence of the complex has been investigated, and the result reveals that it displays luminescent property in the voilet region.

Synthesis, Crystal Structure, and Magnetic Properties of a New Dinuclear Iron Complex with Schiff Base Ligand

A new dinuclear iron（Ill） complex has been synthesized and structurally charac- terized by X-ray crystallography： [Fem2（L）（C6HsCOO）（SO4）（CH3OH）2]·CH3CN＇CH3OH （1, H3L = N,N＇-bis（salicylidene）q,3-diamino-2-propanol）. Complex 1 belongs to orthorhombic space group Pna21 with a= 11.4400（8）, b = 22.9705（2）, c = 12.5712（9）A, V= 3303.5（4）A3, Z= 4, F（000） = 1576, Dc= 1.531 g·cm-3, Mr= 761.36,μ = 1.007 mm-1, S = 1.014, the final R= 0.0505 and wR= 0.1018. The crystal packing is stabilized by intermolecular O-H…O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters ofJ= 19.7 cm-1, g = 1.89 and R2 = 0.9999.

Synthesis,Crystal Structure and Antitumor Activity of a New Zn(Ⅱ) Complex Based on N-Acetyl-L-phenylalanine and 1,10-Phenanthroline

A new Zn（Ⅱ） complex, [Zn（L）2（phen）（H2O）]（1, HL = N-acetyl-L-phenylalanine, phen = 1,10-phenanthroline） has been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction analysis. The Zn（Ⅱ） complex belongs to monoclinic, space group P21 with a = 12.6749（13）, b = 5.5965（6）, c = 22.985（2） A, β = 104.296（2）°, V = 1580.0（3） A^3, Z = 2, Mr = 676.02, Dc = 1.421 μg·m^（-3）, μ = 0.833 mm^-1, F（000） = 704, and the final R = 0.0460, wR = 0.0899 for 4422 observed reflections with I 〉 2σ（I）. The molecules form a 1D chained structure by hydrogen bonds. The antitumor activities of Zn（Ⅱ） complex against human hepatoma SMMC-7721 cells, human lung adenocarcinoma A549 cells and human colon carcinoma WiDr cells have also been investigated.

Synthesis,Crystal Structure and Photoluminescent Property of a New Zn(Ⅱ)Complex Based on 3,4-Bis(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole

The coordination polymer [Zn1.5（2,2？,4？？-tpt）（tpa）2]n （2,2？,4？？-tpt = 3,4-bis（2- pyridyl）-5-（4-pyridyl）-1,2,4-triazole, H2tpa = terephthalic acid） has been obtained by solution evaporation method and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The title compound crystallizes in the triclinic system, space group P , with a = 10.331（3）, b = 10.596（1）, c = 14.966（3） ？, β = 99.029（0）o, V = 1448.86（6） ？3, Z = 2, Dc = 1.668 g/cm3, μ = 1.320 mm-1, F（000） = 740, R = 0.0359 and wR = 0.0841 with I 〉 2σ（I））. In this polymer, the asymmetric unit contains two crystallographically independent Zn（II） ions in different coordination environments. Zn（1） ion is five-coordinated, forming a distorted tetragonal pyramidal geometry, while the Zn（2） ion is six-coordinated to get a distorted octahedral geometry. Each Zn（II） ion is linked by 2,2？,4？？-tpt and H2tpa ligands, forming an infinite 2D structure. The existence of O（8）–H（8）？？？O（2） hydrogen bonding interactions leads the 2D chains to generate a 3D structure. In addition, 1 shows strong photoluminescent emissions in the solid state at room temperature, so it can be used as potential optical materials.

Synthesis,Crystal Structures and Intermolecular Magnetic Coupling Mechanism of the Mononuclear Radical Complex[1-N-methyl-1,10-phenanthrolium][Ni(dmit)_2]

The mononuclear radical anionic complex [1-N-methyl-1,10-phenanthrolium][Ni（dmit）2]（dmit = 1,3-dithiole-2-thione-4,5-dithiolate） with a new countercation has been prepared and its crystal structure was determined by X-ray crystallography at 298 and 80 K. In the mononuclear radical anionic complex, the nickel ion assumes a slightly distorted square-planar geometry. There are two and three kinds of intermolecular interactions between adjacent mononuclear radical anionic complexes in the crystal at 298 and 80 K, respectively（i.e., Models A and B at 298 K; and Models C, D and E at 80 K）. The variable-temperature magnetic moments indicate a strong antiferromagnetic interaction between the adjacent mononuclear radical anionic complexes, and the theoretical calculations reveal that the stronger antiferromagnetic coupling strength at lower temperature should be contributed to the larger overlap integrals between the short contact atoms. This study is the first to reveal the mechanism of stronger magnetic coupling strength at lower temperature for a mononuclear radical anionic nickel complex with dmit as the ligand.

Synthesis,Crystal Structure and Theoretical Calculations of a Cadmium Complex Containing 3-Hydroxybenzoic Acid and 1,4-Bis(imidazol-1-yl)-butane

A new complex [Cd（hba）2（bib）]n·nH2O（1,Hhba = 3-hydroxybenzoic acid,bib = 1,4-bis（imidazol-1-yl）-butane） has been hydrothermally synthesized and characterized by elemental analysis,IR spectrum,thermogravimetric analysis,fluorescence spectrum,and singlecrystal X-ray diffraction.Yellow crystal crystallizes in the orthorhombic system,space group Pbca with a = 16.220（5）,b = 14.980（5）,c = 20.521（5） ？,V = 4986（3） ？~3,C（24）H（26）CdN4O7,Mr = 594.89,Dc = 1.585 g/cm^3,μ（Mo Kα） = 0.927 mm^（-1）,F（000） = 2416,Z = 8,the final R = 0.0242 and w R = 0.0589 for 4076 observed reflections（I 〉 2s（I））.In 1,the Cd（Ⅱ） ion takes a six-coordination mode,and bib ligand bridges adjacent Cd（Ⅱ） ions to generate 1D zigzag chains; these neighboring chains are connected by O–H···O hydrogen bonding interactions,producing a 2D folded layered structure.Furthermore,by O–H···O hydrogen bonding between layers and layers,a 3D supramolecular architecture is formed.In addition,we analyzed Natural Bond Orbital（NBO） in using the PBE0/LANL2 DZ method built in Gaussian 03 Program.The calculation results indicated obvious covalent interaction between the coordinated atoms and Cd（Ⅱ） ion.

Synthesis,Crystal Structure and Fluorescent Properties of Silver and Cadmium Complexes

Two new complexes [Ag（bix）]n·n NAA·n H2O（1） and [Cd（NAA）（phen）2（H2O）]2· 2CH3COO-·H2O（2）（bix = 1,4-bis（imidazol-1-ylmethyl）benzene,HNAA = α-naphthylacetic acid,phen = 1,10-phenanthroline） have been successfully synthesized under hydrothermal conditions.Their structures have been determined by elemental analyses,IR spectroscopy,TG and single-crystal X-ray diffraction analysis.The intermolecular hydrogen bonding or π-π stacking interactions extend the complexes into a 3D supramolecular structure.Moreover,the luminescent properties of complex 2 have been investigated in the solid state.