Syntheses, Crystal Structures and Fluorescence Properties of Two Pb(Ⅱ) 1-Naphthoate Complexes

Two new 1-naphthoate-based Pb（Ⅱ） complexes, [Pb（phen）（NA）2]n 1 and [Pb（bpp）（NA）2]n 2 （NA = 1-naphthoate, phen = 1,10-phenanthroline, and bpp = 1,3-bi（4-pyri- dyl）propane）, were hydrothermally synthesized and structurally characterized. 1 is of monoclinic system, space group C2/c with a = 28.114（3）, b = 10.9601（10）, c = 8.6843（8） , β = 93.3760（10）°, V = 2671.3（4） 3, Dc = 1.814 g/cm3, Mr = 729.73, Z = 4, F（000） = 1416, μ = 6.360 mm-1, the final R = 0.0346 and wR = 0.0948 for 2184 observed reflections with I 〉 2σ（I）. Complex 2 crystallizes in monoclinic, space group C2/c with a = 26.491（2）, b = 8.7773（6）, c = 27.893（2） , β = 113.3020（10）°, V = 5956.8（8）3, Dc = 1.668 g/cm3, Mr = 747.78, Z = 8, F（000） = 2928, μ = 5.706 mm-1, the final R = 0.0211 and wR = 0.0493 for 3677 observed reflections with I 〉 2σ（I）. Both complexes present one-dimensional （1-D） zigzag chains extended by anionic NA linkers for 1 and bridged by neutral bpp connectors for 2, which are further aggregated into 2-D supramolecular networks by interchain π···π stacking interactions. In addition, the two solid-state complexes exhibit different strong emissions at room temperature, suggesting their potential applications as fluorescence materials.

Hydrothermal Syntheses,Crystal Structures,and Characterization of Two Zinc(Ⅱ)Complexes Containing Flexible Bis(benzimidazole)Ligands

Two zinc（II） complexes, namely, [Zn（L1）Cl2]2 （1） and {[Zn（L2）（tbta）]·3H2O}n （2） （L1 = 1,3-bis（2-methylbenzimidazol-1-ylmethyl）benzene, H2tbta = tetrabromoterephthalic acid, L2 = 1,3-bis（2-methylbenzimidazol-1-yl）-2-propanol） have been successfully obtained under hydrothermal conditions. Complex 1 displays binuclear structure which is further extended into a 1D supramolecular chain through π–π stacking. Complex 2 features 2D （4,4） network based on L2/tbta2– double linker. The thermal stability, fluorescence properties and catalytic activities of two complexes for degradation of Methyl orange in a Fenton-like process were discussed.

Hydrothermal Syntheses and Crystal Structures of Two Complexes with 3,5-Dinitrosalicylate and 2,2′-Bipyridine Ligands

The two title complexes, [Cd{3,5-（NO2）2sal}（2,2′-bipy）]n 1 and [Mn{3,5- （NO2）2sal}（2,2′-bipy）]n 2 （3,5-（NO2）2sal = 3,5-dinitrosalicylate, 2,2＇-bipy = 2,2′-bipyridine）, were synthesized by the hydrothermal reaction and structurally characterized. Complex 1 crystallizes in triclinic, space group P1, a = 5.581（4）, b = 12.071（8）, c = 12.88（1）A, α= 92.10（3）,β= 96.73（3）, γ = 102.02（2）°, C17H10N407Cd, Mr = 494.69, V= 841（1）A3, Z = 2, Dc = 1.954 g/cm3, F（000） = 488, μ= 1.353 mm^-1, R = 0.0248 and wR = 0.0761. Complex 2 crystallizes in monoclinic with space group P21/c, a = 8.604（3）, b = 23.88（1）, c = 8.894（3） A, β = 102.45（1）°, C17H10N407Mn, Mr = 437.23, V= 1785（1） A3, Z=.4, Dc = 1.627 g/cm3, F（000） = 884, μ = 0.791 mm^-1, R = 0.0471 and wR = 0.1250. Complex 1 possesses an infinite 1D polymeric chain structure consisting of the repeated basic four-membered ring units （Cd2O2） and eight-membered ring units （CdOCO）2. Compound 2displays a linear 1D chain through Mn（Ⅱ） atoms and bridging carboxylate groups of 3,5-dinitrosalicylic acid ligands with the Mn…Mn separation of 4.472（2）A. The fluorescence properties and cyclic voltammetric behaviors of the complexes are also reported.

Syntheses, Crystal Structures and Properties of Lanthanide（Ⅲ） Complexes with N-Protected Aminoacid of N-p-Tosylglycinate

Complexes { [Ln（H20）2（TsGlyH）a]m·nH2O}∞ （Ln=La （1）, m=2, n=6; Nd （2）, m=2, n=7; Eu （3）, m=2, n= 0; Gd （4）, m=2, n=2; Er （5）, m=3, n=5 and Yb （6）, m=3, n=0, TsGlyH=N-p-tosylglycine monoanion）, have been prepared and characterized by IR spectra, elemental analysis, and TG-DTG 4 and 5 were structurally determined by X-ray diffraction analysis, showing that both of them are comprised of a one dimensional chain structure established via the coordination of μ-carboxylate groups from N-p-tosylglycinate to the corresponding lanthanide（Ⅲ） ions. The one dimensional chains were found inclined to form two-dimensional network via hydrogen bonding and then three dimensional network structure via non-classical hydrogen bonding. The fluorescence spectra of them revealed that the fluorescence of the ligand was quenched by Ln（Ⅲ） ions. In the tested biological activity experiments, they behaved inhibiting effects against the growth of bacteria, indicating that it is a potential medicament worthy of further investigation.

Three Zinc(Ⅱ) Complexes Based on 2-Carboxylic Acid-4-nitropyridine-1-oxide: Synthesis, Crystal Structure, and Fluorescence Properties

Three new metal-organic complexes, namely [Zn(POA)2(H2O)2](1), [Zn(POA)2(H2O)2]·2H2O(2) and [Zn(POA)2]n(3), have been synthesized by organic ligand 2-carboxylic acid-4-nitropyridine-1-oxide(POA) and zinc(Ⅱ) ions. The structures of complexes 1~3 are characterized by single-crystal X-ray analysis, XRD powder diffraction analysis, infrared spectroscopy and thermal stability analysis method. Complex 1 belongs to monoclinic system, space group C2/c with a = 22.8215(15), b = 7.5613(16), c = 10.048(3) ?, β = 109.47°, V = 1634.7(6) ?~3, Z = 4, F(000) = 944, Dc = 1.900 g/cm^3, C(12)H(10)N4O(12)Zn, Mr = 467.61 and μ = 1.584 mm^(-1). The whole molecule presents "V" shape. Complex 2 is a centrosymmetric structure in triclinic system with space group P1: a = 7.4728(5), b = 7.6825(6), c = 8.5184(6) ?, α = 65.975(2), β = 79.87(2), γ = 89.855(2)°, V = 4384.1(5) ?~3, Z = 1, F(000) = 256, Dc = 1.908 g/cm^3, C(12)H(14)N4O(14)Zn, Mr = 503.64 and μ = 1.492 mm^(-1). Complex 3 is a one-dimensional chain structure belonging to monoclinic system and space group P21/c with a = 4.9456(6), b = 12.5322(14), c = 11.2514(13) ?, β = 97.313(11)°, V = 6916.8(14) ?~3, Z = 2, F(000) = 432, Dc = 2.072 g/cm^3, C(12)H6N4O(10)Zn, Mr = 431.58, and μ = 1.852 mm^(-1). In three complexes, six oxygen atoms from the surrounding coordination atoms form a ZnO6 distorted octahedral coordination geometry around the zinc ions. Meanwhile, fluorescent properties of the three complexes were investigated at room temperature. The fluorescence spectroscopic analysis demonstrated that the ligand POA shows red-shift after coordinating with the zinc(Ⅱ) ions.

Synthesis, Crystal Structures and Properties of Two Novel Co（Ⅱ） and Cd（Ⅱ） Complexes of N-AcetyI-L-glutamic Acid and Imidazole Ligands

Two novel complexes {[Co（A-glu）（Im）2]·0.5H2O}n （1） and [Cd（A-glu）（Im）3]n （2） （H2A-glu=N-acetyl-L-glutamic acid, Im=imidazole） have been synthesized from the reaction of H2A-glu with Co（CH3COO）2·4H2O or Cd（CH3COO）2·2H2O in the presence of Im. Both of the complexes display different coordination environment and similar one-dimensional chain structure. The magnetic susceptibility measurements for 1 show a weak antiferromagnetic interaction between two cobalt（Ⅱ） ions bridged by A-glu ligand. The complex 2 exhibits an intense fluorescent emission in solid state at room temperature.

Synthesis,Fluorescence and Magnetic Properties of a New Europium(Ⅲ)Complex Eu(C14H9O3)2(C12H8N2)2(NO3)

A new europium(III)complex Eu(CHO)(CHN)(NO)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/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm,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:~5D→~7F(594 nm)and ~5D→~7F(618 nm).In addition,its XT decreases from 1.29767 cm~3?mol?K at 300 K to 0.01531 cm~3?mol?K at 2 K.

Crystal Structure,Electrochemical and Fluorescent Properties of a New Cadmium(II) Complex[Cd(C_(12)H_6O_4N_2)(Phen)_2(H_2O)]·3H_2O

A new Cd（II） complex [Cd（C12H6OaN2）（Phen）ffH2O）]＇3H2O with 2,2＂-bipyridine- 3,3＂-dicarboxylic acid as a ligand has been synthesized. Crystal data for the title complex are as follows： monoclinic, space group P2dn, a = 12.8458（5）, b = 17.9131（7）, c = 15.2960（6） A, β = 111.7430（10）°, V = 3269.3（2） A3, Dc = 1.581 g/cm3, Z = 4,/a（MoKa） = 0.731 mm-1, F（000） = 1580, the R = 0.0244 and wR = 0.0605. In the title complex, the central Cd（ll） ion is located in a distorted octahedral coordination environment. The electrochemical and fluorescent properties of the title complex were studied. The results show that the electron transfer of the title complex is irreversible in the electrode reaction and it has a broad emission peak in the range of 470-508 nm with the excitation wavelength of 488 nm.

Crystal Structure and Magnetic and Fluorescent Properties of a New Copper(Ⅱ) Complex Cu_2(L)_4(2,2'-bipy)_2(H_2O)_2

A new copper（II） complex Cu2（L）a（2,2＇-bipy）2（H2O）2 （1） has been synthesized with 2-benzoylbenzoic acid （HL） and 2,2＇-bipyridin as ligands. The crystal belongs to a monoclinic system with space group Cc, a = 13.9979（II）, b = 15.9888（13）, c = 30.306（3） A, β = 100.8700（10）°, V= 6661.1（10） A3, Dc= 1.372 g/cm3, Z = 8, F（000） = 2840, the final GOOF = 1.018, R= 0.0685, and wR= 0.1731. There are two mononuclear Cu（L）2（2,2＇-bipy）（H20） units in the crystal of 1. Each Cu（II） cation is coordinated by five atoms. The magnetic and fluorescent properties of 1 were studied. The results show that 1 exhibits weak paramagnetism, and when the excitation wavelength is at 616 nm, it has an intense fluorescent emission band around 482 nm.

Crystal Structure and Electrochemical, Fluorescent and Magnetic Properties of a New Complex [Ag(2,2ˊ-bipy)(C_(14)H_9O_3)]·(C_(14)H_(10)O_3)

A novel silver（I） complex [Ag（2,2ˊ-bipy）（C14H9O3）]·（C14H10O3） has been synthesized with 2-benzoylbenzoic acid as the ligand. Crystal data for the title complex： monoclinic, space group Cc, a = 27.4089（13）, b = 10.2897（5）, c = 12.0024（6）A, β = 111.864（4）°, Mr = 715.49, V = 3141.5（3） A3, Dc = 1.513 g/cm^3, Z = 4, μ（Mo Kα） = 0.694 mm^-1, F（000） = 1456, the final R = 0.0473 and w R = 0.1146. In the title complex, the central Ag（I） ion is located in a triangular coordination environment. The electron transfer is quasi-reversible in the electrode reaction and it shows a strong emission peak in the range of 495-520 nm under 502 nm excitation. In addition, it displays diamagnetic property from 3 to 300 K.

Synthesis,Fluorescence and Magnetic Properties of a New Europium(Ⅲ) Complex Eu(L)3(Phen)2

A new europium（III） complex Eu（L）3（Phen）2（1） with 2-benzoylbenzoic acid（HL） and 1,10-phenanthroline（Phen） as ligands has been synthesized. Crystal data for the complex are as follows： monoclinic, space group P21/c, a = 2.2577（4）, b = 1.23484（19）, c = 1.8789（3） nm, β = 94.918（3）o, V = 5.2189（14） nm^3, Dc = 1.512 g/cm^3, Z = 4, μ（Mo Kα） = 1.269 mm^-1, F（000） = 2408, the final R = 0.0433 and w R = 0.1038. The Eu（III） ion is coordinated by nine atoms to give a single-capped square antiprism coordination geometry. 1 shows two intense fluorescence emission bands arising from the transitions of Eu^3＋： ^5D0→^7F1（597 nm） and ^5D0→^7F2（615 nm） with an excitation wavelength of 396 nm. In addition, 1 displays antiferromagnetic property at low temperature.

Two Praseodymium Coordination Complexes with 1,3-Phenylenediacetate:Structural Diversity Tuned by Auxiliary Ligands

Two new coordination complexes, [Pr（1,3-pda）0.5（nbca）2（H2O）2]（1） and [Pr2（1,3-pda）3（2,2ˊ-bpy）2（H2O）2]（2）（H2pda = 1,3-phenylenediacetic acid, Hnbca = 5-nitro [1,1ˊ-biphenyl]-3-carboxylic acid, 2,2ˊ-bpy = 2,2ˊ-bipyridine）, have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. In 1, the nbca ligands bridge the Pr3＋ ions to form a 1D chain. Moreover, these 1D chains are united together through the 1,3-pda ligands to afford a 2D layer. In contrast, due to a different auxiliary ligand, complex 2 is a 2D layer linked through only bridging deprotonated 1,3-pda. Thermal stabilities and solid fluorescence properties of 1 and 2 were also studied.

Synthesis and Fluorescent, Magnetic and Thermal Stability Properties of a New Europium（Ⅲ） Complex Eu2(C15H11O3)6(C12H8N2)2

A new europium（Ⅲ） complex Eu2(C15H11O3)6(C12H8N2)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, Dc = 1.522 g/cm3, 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(C20H14O3N)3(C12H8N2)（H2O）·H2O

A new terbium(Ⅲ complex Tb(C20H14O3N)3(C12H8N2)（H2O）·H2O 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/cm3, 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 Tb3+: 5D4 → 7F6（491 nm）, 5D4 → 7F5（546 nm）, 5D4 → 7F4（585 nm） and 5D4→7F3（621 nm）. Also reported are the magnetic and thermal stability properties of the complex.

Preparation,Characterization and Properties of Two New Lanthanide(Ⅲ)-5-(2-pyridyl)tetrazolate Complexes

Two new mononuclear lanthanide（Ⅲ） complexes Ln（pytz）3（H2O）3·（H2O）3.5[Ln=Tb（1）;Eu（2）;Hpytz=5-（2-pyridyl）tetrazole] were synthesized by reacting Hpytz with the corresponding lanthanide（Ⅲ） ions and characterized.The single crystal X-ray diffraction analysis reveals that complexes 1 and 2 are isostructural and the lanthanide（Ⅲ） ions in both complexes 1 and 2 are nine-coordinated,with three oxygen atoms of three coordination water molecules and six nitrogen atoms of three pytz ligands,forming a monocapped square antiprism.Extensive hydrogen bonds exist,resulting in a three-dimensional supramolecular network structure by hydrogen-bonds in both complexes 1 and 2,respectively.Complex 1 exhibits typical green fluorescence of Tb（Ⅲ） ion and complex 2 red fluorescence of Eu（Ⅲ） ion,in solid state at room temperature.

Synthesis, Structure, and Luminescent Properties of Two Complexes Based on Flexible Phenylenediacetate Ligand

Two new Zn(Ⅱ) and Cd(Ⅱ) coordination complexes, [Zn(ppda)(idz)]n(1) and [Cd(mpda)(mbib)]n(2)(H2 ppda = 1,4-phenylenediacetic acid, H2 mpda = 1,3-phenylenediacetic acid, idz = imidazole, mbib = 1,3-bis(imidazol-1-ylmethyl)benzene), have been synthesized by using Zn(Ⅱ)/Cd(Ⅱ) salt and phenylenediacetic acid in the presence of different imidazole ligands under hydrothermal conditions, and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography and thermogravimetric analysis. Complex 1 crystallizes in orthorhombic system, Iba2 space group. The carboxylic acid ligands form a 2 D helical layer with Zn(Ⅱ) ions, and such layers are expanded into a 3 D network structure by the force of C–H…π. Complex 2 crystallizes in monoclinic system, P21/n space group. Complex 2 shows a 3 D framework with two Cd(Ⅱ) ions as nodes of a dual-core unit, which can be considered to be 6-connected net and regarded as a rare(44,510,7) topology network with self-interlacing. The structural diversities indicate that rigid and flexible imidazole ligands play dominating roles in modulating the formation of structures of these crystalline materials. Moreover, the luminescent properties of two complexes are investigated in solid state.

Synthesis, Crystal Structure and Optical Properties of a New Nd(III) Nitronyl Nitroxide Complex [Nd(NIT2Py)_2(NO_3)_3]

A new Nd（Ⅲ） nitronyl nitroxide complex [Nd（NIT2Py）2（NO3）3] （NIT2Py = 2-（2＇-pyridyl）-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide） has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 12.396（4）, b =11.134（4）, c = 23.360（7） A°, β = 98.178（6）°, V= 3191.2（18） A°^3, C24H32N9NdO13, Mr = 798.83, Dc =1.663 g/cm^3, μ（MoKa） = 1.704 mm^-1, F（000） = 1612, Z = 4, the final R = 0.0425 and wR = 0.0957 for 6532 independentreflections with Rint = 0.0642 and 4552 observed reflections （I 〉 2σ（I））. The complex exists as discrete mononuclear molecules and the neodymium（Ⅲ） ion is ten-coordinated with three bidentate nitrate anions and two radical ligands （NIT2Py） via bidentate chelating mode.The optical properties of the complex are discussed.

Synthesis and Crystal Structure of a New Praseodymium(Ⅲ)-Copper(Ⅱ)Polymeric Complex:〔Pr_(2)Cu_(3)(L_(1))_(6)〕_(n)(H_(2)L_(1)=NH{CH_(2)COOH}_(2))

A novel polymeric Pr 2Cu 3 complex of iminodiacetic acid (H 2L 1=NH{CH 2COOH} 2) Pr 2Cu 3(L 1) 6 n , 1, has been synthesized and structurally characterized. The title complex Pr 2Cu 3O 24 N 6C 24 H 30 ( M r =1258.97) crystallized in trigonal space group P3 c1 (No. 165) with a = 13.424(4), c=14.752(6); V=2303(1) 3; F(000)=1226; λ (Mo Kα )=35.2 cm -1 ; D c =1.820 g·cm -3 ; Z =2. The final R and R w are 0.072 and 0.081 respectively for 1412 reflections with I】3σ(I) . In crystal 1, the Pr 3+ ion is nine coordinated by 6 O atoms from three bidentate chelating carboxylate groups and 3 O atoms from three anti anti bridging carboxylic groups of six L 1 ligands; the Cu 2+ ion is six coordinated by 4 O and 2 N atoms from two pentadentate L 1 ligands. Each pair of Pr(Ⅲ) atoms is bridged by three L 1 ligands, each of which also chelates with one copper(Ⅱ) ion, thus forming a Pr 2Cu 3 cluster unit. Such cluster units are cross linked by flexible L 1 ligands into a three dimensional coordination framework.

Hydrothermal Synthesis, Crystal Structure and Fluorescent Property of a Cd(Ⅱ) Complex Based on Biimidazole and Isonicotinate-N-oxide

A new complex [Cd（H2biim）2（H2O）2]·（ino）2·4H2O （H2biim = 2,2＇-biimidazole, ino = isonicotinate-N-oxide） has been prepared and characterized by single-crystal X-ray diffraction analysis, IR and fluorescence spectra analysis. The crystal is of triclinic system, space group P1 with a = 7.5380（6）, b = 8.0402（7）, c = 13.5094（11） , α = 104.269（1）, β = 93.604（1）, γ = 98.349（1）°, V = 780.93（11） 3, Mr = 765.00, Dc = 1.627 g/cm3, F（000） = 390, μ = 0.776 mm-1 and Z = 1. The final R = 0.0322 and wR = 0.0825 for 7038 observed reflections with I 2σ（I） and R = 0.0341 and wR = 0.0832 for all data. The title complex exhibits an infinite chain-like structure through bridging isonicotinate-N-oxide. Strong interchain hydrogen bonds between isonicotinate-N-oxide and H2biim result in the robust 3-D supramolecular architecture. Moreover, the complex shows strong photoluminescence with emission maximum at λ = 401 nm upon λex = 330 nm.

Synthesis, Crystal Structure and Fluorescent Property of One New Complex [Na_2(2-benzoylbenzoato)_4(Phen)_2(H_2O)_2]·H_2O

One binuclear sodium（Ⅰ） complex [Na2（2-benzoylbenzoato）4（Phen）2（H2O）2]·H2O has been synthesized with 2-benzoylbenzoic acid and 1,10-henanthroline as ligands. The crystal structure was determined by X-ray diffraction. The crystal belongs to the triclinic system with space group P , a = 1.08096（8）, b = 1.09619（8）, c = 1.09740（8） nm, α = 79.0600（1）, β = 71.0450（1）, γ = 62.0540（1）o, V = 1.08533（1） nm3, Dc = 1.421 g/cm3, Z = 2, F（000） = 484, GOOF = 1.036, the final R = 0.0363 and wR = 0.0961. The crystal structure shows that two neighboring sodium（Ⅰ） ions are linked together by two bridging water molecules, and each end position is coordinated with one 1,10-phenanthroline molecule and one 2-benzoylbenzoato to form a binuclear structure. Each sodium（Ⅰ） ion in the molecule is coordinated with five atoms to give a distorted trigonal bipyramid. The fluorescence property of the title complex is also discussed.