Syntheses, Structures and Fluorescent Properties of Copper（II） and Manganese（II） Helical Complexes Bridged by 4,4＇-Dipyridylsulfide

Two isostructural helical coordination polymers, {[Cu(dps)2(Hssa)-(H2O)2]·3H2O}n (1) and {[Mn(dps)2(Hssa)(H2O)2]·2H2O}n (2), have been synthesized by the solvothermal reaction of dps and H3ssa with CuCl2 or Mn(CH3COO)2 (dps = 4,4'-dipyridylsulfide, H3ssa = 5-sulfosalicylic acid). Both compounds crystallize in monoclinic, space group P21/n. In either complex, the central metal ion (CuII for compound 1 and MnII for compound 2) is surrounded by one Hssa2ˉ ligand, two coordinated aquas and three dps molecules with a N3O3 donor set in a distorted octahedral coordination geometry. Half of the dps is monodentate and another half acts as μ2-bridging ligands. It is through the bridging function of dps that the neighbouring metal centers are connected and a one-dimensional helical structure of compound 1 or 2 forms. Fluorescence studies indicate that compounds 1 and 2 have blue emission bands centered at 403 and 405 nm, respectively.     

Synthesis and characterization of novel heteronuclear complexes of Ln(Ⅲ)-Cu(Ⅱ) with non-cyclic polyether Schiff base

Nine novel heteronuclear complexes of Ln(Ⅲ)-Cu(Ⅱ) with salicylidene tetraethvlcne glycol diamine (SALTTA) have been synthesized and characterized.They have the general formulae [LnCu2(SALTTA)2(NO3)3](NO3)4 3H2O (Ln=La,Pr.Nd,Srn) and [LnCu3(SALTTA)3(NO3)5]-(NO3)4-4H2O (Ln=Gd,Tb,Er,Yb,Y).The IR spectra show that vc=N in the Ln(Ⅲ)-Cu(Ⅱ) het-eronuclear complexes are splitted up into two peaks with a far distance.It has been confirmed that oxygen atoms in oxyethylene of the ligand are not all coordinated to the central metal ions by both IR and NMR methods.     

Synthesis and Crystal Structure of a Novel 1D Coordination Polymer: [Pr(BYBA)3(H2O)2]·[Pr(BYBA)3(H2O)]

The novel coordination polymer [Pr(BYBA)3(H2O)2]·[Pr(BYBA)3(H2O)] (BYBAH = 2-benzoylbenzoic acid) was yielded by hydrothermal synthesis, determined by single-crystal X-ray diffraction, and characterized by FT-IR and UV-Vis spectra. The crystal crystallizes in the triclinic system, space group P with a = 9.112(3), b = 14.644(5), c = 27.076(11) (A), α = 84.223(3), β = 87.816(4), γ = 88.902(4)o, V = 3592(2) (A)3, C84H60O21Pr2, Mr = 1687.14, Z = 2, F(000) = 1700, Dc = 1.560 g/cm3, μ = 1.419 mm-1, the final R = 0.0485 and wR = 0.1258 for 13035 observed reflections with I＞2((I). The compound contains two different building units, [Pr2(BYBA)6(H2O)4] and [Pr2(BYBA)6(H2O)2]. It is noticeable that [Pr2(BYBA)6(H2O)4] is an isolated binuclear building block, in which the Pr3 ion centers are both located in an eight-coordinated environment. However, in [Pr2(BYBA)6(H2O)2] the Pr3 ion centers are located in a nine-coordinated environment and connected by BYBA ligands to form 1D chains.     

Synthesis and Crystal Structure of a Novel 1D Coordination Polymer:[Pr(BYBA)_3(H_2O)_2]·[Pr(BYBA)_3(H_2O)]

The novel coordination polymer [Pr(BYBA)3(H2O)2]·[Pr(BYBA)3(H2O)] (BYBAH=2-benzoylbenzoic acid) was yielded by hydrothermal synthesis,determined by single-crystal X-ray diffraction,and characterized by FT-IR and UV-Vis spectra. The crystal crystallizes in the triclinic system,space group P1 with a=9.112(3),b=14.644(5),c=27.076(11),α=84.223(3),β= 87.816(4),γ=88.902(4)o,V=3592(2)3,C84H60O21Pr2,Mr=1687.14,Z=2,F(000)=1700,Dc= 1.560 g/cm3,μ=1.419 mm-1,the final R=0.0485 and wR=0.1258 for 13035 observed reflections with I > 2σ(I). The compound contains two different building units,[Pr2(BYBA)6(H2O)4] and [Pr2(BYBA)6(H2O)2]. It is noticeable that [Pr2(BYBA)6(H2O)4] is an isolated binuclear building block,in which the Pr3+ ion centers are both located in an eight-coordinated environment. However,in [Pr2(BYBA)6(H2O)2] the Pr3+ ion centers are located in a nine-coordinated environment and connected by BYBA ligands to form 1D chains.     

Three New Zn(Ⅱ)/Cd(Ⅱ) Coordination Polymers Constructed with 2-Mercaptonicotinic Acid and 1,2-Di(4-pyridyl)ethylene: Syntheses and Structure Analysis

Three new Zn(Ⅱ)/Cd(Ⅱ) coordination polymers based on 2-mercaptonicotinic acid (H2mna) with 1,2-di(4-pyridyl)ethylene (dpe) introduced as a bridging ligand have been synthesized via hydrothermal method and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. As reported in this paper, [Zn2(dpe)0.5(mna)2] (1) can be classified as a two-dimensional layer structure in which the 1D chain composed of Zn(Ⅱ) and mna ligands is bridged by dpe ligands, while the complex named [Zn4(dpe)4(mna)4] (2) is a tetra-nuclear cluster compound. These two compounds are further extended to three-dimensional structures by hydrogen bonds along with C-H…π and π…π interactions. Compound 3 with general formular [Cd2(dpe)0.5(mna)2]·H2O belongs to a three-dimensional porous structure in which the 2D metal layers formed by the coordination of Cd(Ⅱ) and mna ligands are connected with the bridging of dpe ligands.     

Synthesis,Structure and Fluorescence of a Copper(II) Complex [Cu_2(bipy)_2(Hpht)_2Cl](Hpht)(bipy=2,2'-Bipyridine,H_2pht=o-Phthalic Acid)

1 INTRODUCTION o-Phthalic acid (H2pht) is a versatile ligand for co-ordinating to metal ions in various modes, such asmonodentate bonding through a carboxylic O atom[1],bidentate fashion via two carboxylic O atoms[2] andtriple coordination through its three carboxylic Oatoms[3], and bridging mode with two or four Oatoms of its carboxylate groups[4]. The coordinationproperties thus allow for the preparation of complex-es with a large variety of architectures, forming iso-lated mono-, di…     

Synthesis and Crystal Sturcture of a New Praseodymium（Ⅲ）polym煳x：[

A novel polymeric Pr2Cu3 complex of iminodiacetic acid (H2L1=NH{CH2COOH}2) [Pr2Cu3(L1)6]n , 1, has been synthesized and structurally characterized. The title complex Pr2Cu3O24N6C24H30 (Mr=1258.97) crystallized in trigonal space group Pc1 (No. 165) with a = 13.424(4), c=14.752(6)(); V=2303(1)()3; F(000)=1226; λ(MoKα)=35.2 cm-1; Dc=1.820 g.cm-3; Z=2. The final R and Rw are 0.072 and 0.081 respectively for 1412 reflections with I>3σ(I). In crystal 1, the Pr3+ 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 L1 ligands; the Cu2+ ion is six-coordinated by 4 O and 2 N atoms from two pentadentate L1 ligands. Each pair of Pr(Ⅲ) atoms is bridged by three L1 ligands, each of which also chelates with one copper(Ⅱ) ion, thus forming a Pr2Cu3 cluster unit. Such cluster units are cross-linked by flexible L1 ligands into a three-dimensional coordination framework.     

Crystal structures and thermal decomposition mechanism of four lanthanide complexes with halogen-benzoic acid and 1,10-phenanthroline

This paper describes syntheses and structure determination of four lanthanide complexes [Nd(2-Cl-4-FBA) 3 phen] 2 (1, 2-Cl-4-FBA = 2-chloro-4-fluorobenzoate, phen = 1,10-phenanthroline), [Ln(2,5-DClBA) 3 phen] 2 (Ln = Sm(2) and Tb(3), 2,5-DClBA = 2,5-dichlorobenzoate) and [Sm(2-Cl-4,5-DFBA) 3 (phen)(H 2 O)] 2 (4, (2-Cl-4,5-DFBA = 2-chloro-4,5-difluorobenzo- ate). The complexes were characterized by elemental analysis, infrared and ultraviolet spectra, and X-ray single-crystal diffraction. In the molecular structures of 1 4, two Ln 3+ ions are linked by four carboxyl groups, with two of them in a bridging bidentate mode and the other two in a bridging-chelating tridentate mode, forming four binuclear molecules. In addition, each Ln 3+ ion is also chelated to one phen molecule and one carboxyl group in the complexes, except each Sm 3+ ion in 4 which is bonded to one carboxyl group by unidentate mode and one H 2 O molecule. There are two different coordination polyhedrons for each Nd 3+ ion in the two similar molecular structures of 1 and they are a distorted monocapped square antiprismatic and a distorted tricapped triangular prism conformation, respectively. The coordination polyhedron for each Ln 3+ ion in 2 4 is a nine-coordinated distorted mono-capped square antiprismatic conformation. The complex 3 exhibits green luminescence under the radiation of UV light. The thermal decomposition behaviors of the complexes have been discussed by simultaneous TG/DSC-FTIR technique. The 3D surface graphs for the FTIR spectra of the evolved gases were recorded and the gaseous products were identified by the typical IR spectra obtained at different temperatures from the 3D surface graphs. Meanwhile, we discussed the nonisothermal kinetics of 1 4 by the integral isoconversional non-linear (NL-INT) method.     

A Novel Two-dimensional Lead(Ⅱ) Coordination Polymer Based on Dinuclear Lead(Ⅱ) Unit Containing(5-Chloro-quinolin-8-yloxy) Acetate

A novel two-dimensional lead(II) coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand(5-chloro-quinolin-8-yloxy)acetic acid(HL) with PbCl2, and its structure was characterized by IR, elemental analysis, TG-DTA and single-crystal X-ray diffraction analysis. The crystal is of monoclinic system, space group P21/c with a = 16.7603(7), b = 8.6907(4), c = 8.4745(3), β = 101.1110(11)°, C11H7Cl2NO3 Pb, Mr = 479.27, V = 1211.25(9)3, Z = 4, Dc = 2.628 g/cm3, F(000) = 880, μ = 14.367 mm-1, R = 0.0173 and wR = 0.0508. The asymmetric unit contains one lead(II) cation, one(5-chloro-quinolin-8-yloxy)acetate(L) ligand and a chloride ion. The PbII center is hepta-coordinated in a distorted pentagonal bipyramidal geometry. The coordination sphere of the Pb atom is completed by two oxygen atoms and one nitrogen atom of the same L ligand, two bridging chloride ions and two bridging oxygen atoms of two adjacent L ligands. Two PbII centers are linked by the two L ligands to form a C2-symmetric dimer unit with a planar [Pb2O2] ring. Each dimer unit acts as a secondary building unit(SBU) and links adjacent four dimer units by the chloride atoms and oxygen atoms of carboxylate groups of L, forming a two-dimensional array. Such two-dimensional layers are packed through intermolecular C–H···Cl hydrogen bonds into a three-dimensional supramolecular structure. When the dimer unit is viewed as a 4-connected node, 1 is simplified as a 4-nodal 2-D network with square lattices of the diagonal lengths to be 6.079(1). The fluorescence emission peak of complex 1 appears near 407 nm.     

Synthesis and Characterization of Two Binuclear Macrocyclic Zinc(Ⅱ) Complexes by Anion Exchange

Two macrocyclic zinc(II) complexes {[ZnL(VO3)2]·0.33H2O}n(1) and [ZnL(H2O)2][Ni(CN)4](2)(L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) have been obtained from the reactions of [ZnL](ClO4)2 with NH4VO3 and K2[Ni(CN)4], respectively, and structurally characterized by elemental analysis, IR, XRPD, TG and X-ray diffraction. Single-crystal X-ray diffraction analyses indicated that the Zn(II) atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic ligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedra in the axial positions in 1, and two oxygen atoms of two water molecules in 2. Complex 1 shows a three-dimensional structure, which is constructed by the links of [VO3]nn- chains with [ZnL]2+, forming one-dimensional channels occupied by guest water molecules. The monomers of [ZnL(H2O)2]2+ and [Ni(CN)4]2- are connected through the intermolecular hydrogen bonds to form a two-dimensional sheet in complex 2.     

Crystal structure and thermal decomposition mechanism of the supramolecular complex of barium chloride with inositol

The single crystal of [Ba(H2O)2(C6H12O6)2Cl2] was obtained based on the phase equilibrium results. Its structure was determined by X-ray crystallographic analysis. The crystals are monoclinic and in space group C2/c with a=1.901 7(2) nm, b = 0.682 13(8) nm, c = 0.162 60(2) nm,β=96.593(2)°and V= 2.095 3(4) nm3, Z= 4, DC=1.917 g·cm-3. In its solid state, this supramolecular complex is a three-dimensional network with double layers connected by hydrogen bondings. The molecule structure of [Ba(H2O)2(C6H12O6)2Cl2] has a central barium ion that is coordinated to two water molecules, two chlorides, and four hydroxyls from the two inosi-tols. Losing the coordinating water is controlled by random nucleation and growth mechanism (n = 2/3) and 3-dimensional diffusion mechanism (n=2).     

Synthesis and Crystal Structure of a Novel 3D Inorganic-organic Hybrid Metallic Coordination Polymer, [Na2Cd（2,6-pyda）（N3）2（H2O）6]n

A novel coordination polymer [Na2Cd（2,6-pyda）（N3）2（H2O）6]n （2,6-H2pyda = 2,6- pyridinedicarboxylic acid） has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c, with a = 24.416（4）, b = 10.7638（17）, c = 6.9224（11） A^°, β= 106.124（2）A^°, V = 1747.7（5） A^°3, Mr = 515.64, De= 1.960 g/cm^3,μ = 1.365 mm^-1, F（000） = 1024, Z = 4, the final R = 0.0426 and wR = 0.1320. In the title complex, there exist two kinds of metal centers in the structure, cadmium ions and sodium ions. The Cd（Ⅱ） atom shows a distorted pentagonal-dipyramidal geometry defined by two O and one N atoms from one deprotonated pyda ligand and four N atoms from four μ-1,1,3 azido groups. The adjacent cadmium atoms are bridged via two μ-1,1,3 azido groups, along the c axis to afford an extended chain. There is also a 2D network which is comprised of binuclear subunits [NaE（H2O）6] connected by O atoms from coordinated water between the adjacent Cdn（pyda）n（Na）2n infinite chains. Furthermore, each cadmium atom is connected with four adjacent sodium atoms through the bridging N3- ligand in μ-1,3 patterns. Thus, the title complex exhibits a novel three-dimensional network structure.     

Synthesis and Structure Investigation of a Transition Metal Ion Bridging Bis(diphosphopentamolybdates),[H_2BIIM]_3[HBIIM]_4[Mn(H_2O)_4(P_2Mo_5O_(23))_2]·7H_2O

A novel transition metal ion bridging bis(diphosphopentamolybdates) has been synthesized and characterized by elemental analysis,IR spectrum,UV spectrum and single-crystal X-ray diffraction.The single-crystal structure analysis shows that the compound consists of seven charge-compensating 2,2'-biimidazole cations (BIIM=2,2'-biimidazole) and one dumbbell-like [Mn(H2O)4(P2Mo5O23)2]10-heteropolyanion which is constructed by two [P2Mo5O23]6-clusters bridged through one [Mn(H2O)4]2+ cation.     

Mononuclear and Dinuclear Yttrium Complexes Supported by Pyrrolide Ligands: Syntheses,Structures and Catalytic Behaviors towards the Ring-opening Polymerization of ε-Caprolactone

The syntheses, structures and catalytic activities of two yttrium complexes supported by pyrrolide ligands are reported. Treatment of Y(N(Si Me3)2)3 with one equivalent of H3bptd(H3bptd = 1,9-bis(2-pyrrolyl)-2,5,8-triazanona-1,8-diene) in THF gave a complex of composition [Y(bptd)(THF)]2(1). Reaction of Y(N(Si Me3)2)3 with one equivalent of H3tpa(H3tpa = tris(pyrrolyl-?-methyl)amine) in THF generated [Y(tpa)(THF)3](2) in good yield. Complexes 1and 2 have been characterized by single-crystal X-ray diffraction, elemental analyses and NMR spectroscopy. Complex 1 is dinuclear. The two metal centers are doubly bridged by two amine nitrogen atoms to form a Y–N–Y–N four-membered rhombus ring. The geometries of Y3+ ions in 1and 2 are well described as pentagonal bipyramid and capped octahedron, respectively. The ring-opening polymerization reactions of ?-caprolactone initiated by 1 and 2, respectively, were investigated. They both exhibited good catalytic activity for the polymerization of ?-caprolactone. All of the obtained polymers have high molecular weights and relatively narrower PDIs. The polymers generated by 2 possessed polydispersity close to 1.1. The good catalytic activities of 1 and 2 reveal their potential applications in polymer industry.     

Syntheses and Crystal Structures of Mono-and Binuclear Copper(Ⅱ) Mixed-ligand Complexes Involving Schiff Base

1 INTRODUCTION The chemistry of copper compounds has been extensively investigated and the relationship be- tween structure and reactivity, ranging from indus- trial catalysis to biochemistry activity, is of major importance. For binuclear copper(II) complexes equa- torially bridged by pair of hydroxide[1] or alkoxide[2, 3] groups, satisfactory linear correlation is found be- tween the Cu–O–Cu bridging angle and spin coupling between the metal centers. However, for binuclear copper(I…     

Synthesis,Crystal Structure and Antimicrobial Activity of {[Bis(pyridine-κN)bis(3,5-dinitrosalicylato κ-O,O')Zn(Ⅱ)][bis(pyridine-κN)Zn(Ⅱ)]}

A novel {[bis(pyridine-κN)bis(3,5-dinitrosalicylato κ-O,O')Zn(Ⅱ)][bis(pyridine-κN)Zn(Ⅱ)]}(C_(34)H_(24)N_8O_(14)Zn_2) was synthesized by a self-assemble method at room temperature. The molecular structure was determined by single-crystal X-ray analysis. The compound crystallizes in the monoclinic system, space group P2_1/n with a = 12.2156, b = 13.5696, c = 22.5602 ?, β = 90.061o, Z = 4 and V = 3739.6(3) ?~3. The new 1D binuclear coordination polymer {[bis(py-κN)bis(3,5-dinitrosal κ-O,O′) Zn(Ⅱ)][bis(py-κN)Zn(Ⅱ)]} resulted from two different types of moieties. The polymer [bis(py-κN)bis(3,5-dinitrosal κ-O,O′)Zn(Ⅱ)] unit is connected with [bis(py-κN) Zn(Ⅱ)] by zigzag topology. One zinc(Ⅱ) cation has a six-fold coordination environment, in which the metal atom is connected with four oxygen atoms of two 3,5-dinitrosalicylic acids to form equatorial bonds and two nitrogen atoms of pyridine to generate the axial bonds. Other four-fold nucleus contain two Zn–O bonds from different 3,5-dinitrosalicylic acids and two bonds with the Natom of pyridine. Antimicrobial assay results indicated that the compound showed moderate activities against different bacterial and fungal strains.     

1D Lanthanide Coordination Polymers Based on 3-（Pyridin-4,yl）benzoic Acid： Syntheses, Structures and Luminescent Properties

Four novel 1D lanthanide coordination polymers with formula [Ln(3,4-pybz)3(H2O)2· H2O]n (Ln = 1 Sm; 2 Eu; 3 Tb; 4 Dy, 3,4-Hpybz = 3-(pyridin-4-yl)benzoic acid) have been synthesized by hydrothermal reactions of lanthanide oxide and 3-(pyridine-4-yl) benzoic acid. Single-crystal X-ray diffraction shows that the four compounds are isostructural. They all crystallize in a monoclinic system, space group P1. They have a doubly carboxylate-bridged infinite-chain structure with alternating Ln-(carboxylate)2-Ln linkages and one chelating carboxylate group on each metal center. The Ln ion also combines to two water molecules to form an eight-coordinate square antiprismatic geometry. The pyridine nitrogen atoms of the ligand do not coordinate to the metal centers but direct the formation of a 3D network through hydrogen bonding with coordinated water molecules. The photoluminescent properties of 2 and 3 have been also studied.     

Synthesis and Structure of Dibenzoyl-bissemicarbazone Neodymium(Ⅲ) Perchlorate

A new Schiff base Dibenzoyl-bissemicarbazone C15H16N6O2(L) and its complex with neodymium(Ⅲ ) perchlorate [NdL2(H2O)2](ClO4)3 were synthesized. The crystal and molecular structure of the title complex were determined by single crystal X-ray diffraction. The crystal is monoclinic and conforms to space group P. with cell constants a=10. 893(2) A, b= 12. 118(3) A , c=22. 494(5) A , β=89. 86(3)% V = 2969.19A3. The final standard deviation R=0. 0919. In the complex Nd is coordinated by four nitrogen and six oxygen atoms, of which four nitrogen and four oxygen atoms are provided by two neutral ligands L, and the other two oxygen atoms are provided by two water molecules, forming a ten-coordinated complex cation, which the perchlorate groups exist in the outer sphere. The coordination polyhedron takes a bicapped anti-square prism arrangement. That the average bond length of Nd-N is 2. 735 A indicates that the coordination of N in groups to Nd( Ⅲ ) is very weak.     

Synthesis, Crystal Structure and Properties of a Europium Complex with 3-Iodobenzoic Acid and 2,2′-Bipyridine

The complex [Eu(3-IBA)3·2,2'-bipy]2 was synthesized from 3-iodobenzoic acid (3-HIBA), 2,2'-bipyridine (2,2'-bipy) and EuCl3·6H2O by hydrothermal synthesis, and its crystal structure was determined by X-ray single-crystal diffraction. It is of triclinic, space group P, with a = 10.958(2), b = 12.311(3), c = 12.556(3) (A), α = 81.549(3), β = 82.404(4), γ = 78.348(3)°, Mr = 1049.15, V = 1631.7(6) (A)3, Z = 1, Dc = 2.135 g/cm3, F(000) = 980, λ(MoKα) = 0.71073 A, μ(MoKα) = 4.804 mm-1, the final R = 0.0329 and wR = 0.0723 for 4640 observed reflections with I ＞ 2σ(I). The Eu(Ⅲ) ion is eight-coordinated and two Eu(Ⅲ) ions are held together by four 3-iodobenzoate groups in the bidentate bridging mode. The complex was characterized by DTA-TG, IR, UV and fluorescence spectra.     

Synthesis, crystal structure and magnetic properties of a novel manganese(II)-nitronyl nitroxide-azido(μ_(1,1) and μ_(1,3)) one-dimensional complex

A novel one-dimensional manganese(Ⅱ) complex containing nitronyl nitroxide radical [Mn2(IM2-py)2(Ac)2((μ1.1-N3)(μ1,3-N3) . EtOH]n was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group p21/n. Each Mn(Ⅱ) ion is six-coordinated in a distorted octahedral environment. The two N atoms of the nitronyl nitroxide radical and the two O atoms of acetate ligands are in the equatorial plane, whereas the two different azido bridging ligands are in trans axial position. Mn(Ⅱ) ions are linked by nitrogen atom of μ1,1-azido and oxygen atoms of two carboxy groups to form a Mn-Mn unit. Mn-Mn units are linked by azido ligands through u1,3 bridging style to form a one-dimensional chain. The compound is connected by the coordination bonds,π-π interactions and hydrogen bonds as a three-dimensional structure. Magnetic susceptibility data support that there are stronger antiferromagnetic interactions between the radical and Mn(Ⅱ) ion, weak antiferromagnetic inter