Syntheses,Crystal Structures and Luminescent and Magnetic Properties of Cerium(Ⅲ) and Zinc(Ⅱ) Coordination Compounds Constructed from 3,5-Dibromobenzoic Acid

Two coordination compounds, namely [Ce(3,5-Br2BC)3(3,5-HBr2BC)]n(1) and [Zn(3,5-Br2BC)2(phen)](2, 3,5-HBr2 BC = 3,5-dibromobenzoic acid, phen = 1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a 1D chain coordination network, which is further extended into a 3D supramolecular architecture via Br···Br and Br···O halogen bonding. Compound 2 consists of a mononuclear molecule, which is assembled to a 3D supramolecular framework through C–H···O hydrogen bond, π-π stacking interactions and Br···π halogen bonding. Luminescent and magnetic properties of both compounds have also been studied.     

Synthesis,Crystal Structure and Antitumor Activity of a Na(Ⅰ) Coordination Polymer Based on 2-Propyl-4,5-imidazoledicarboxylic Acid and 1,10-Phenanthroline Ligands

A new Na(I) coordination polymer, [Na2(Hpimdc)(H2 pimdc)(phen)2]n(1), has been synthesized by the reaction of NaOH with 2-propyl-4,5-imidazoledicarboxylic acid(H3 pimdc)and 1,10-phenanthroline(phen). The Na(I) coordination polymer 1 was characterized by single-crystal X-ray diffraction analysis and elemental analysis. In 1, the bridged ligand H3 pimdc adopts two modes(singly deprotonated and doubly deprotonated) to coordinate with the Na(I) ion.The Na(1) ion is six-coordinated with three N atoms from a phen ligand and a H2 pimdc ligand,three O atoms from a Hpimdc ligand and two other different H2 pimdc ligands. The Na(2) ion is also six-coordinated with three N atoms from a phen ligand and a Hpimdc ligand, three O atoms from a H2 pimdc ligand and other two different Hpimdc ligands. Complex 1 exhibits a 1 D chain structure built up by μ-H2 pimdc-and μ-Hpimdc2-ligands. The antitumor activities of complex 1 against human SGC7901, A549 and H08910 cells have been tested.     

Syntheses,Crystal Structures and Luminescent Properties of Lead(Ⅱ) and Cadmium(Ⅱ) Coordination Polymers Constructed from Biphenyl-2,5,3′-tricarboxylate

Two coordination polymers, namely [Pb(Hbtc)(phen)]n(1) and {[Cd3(btc)2(H2O)4]·2H2O}n(2, H3btc = biphenyl-2,5,3'-tricarboxylic acid, phen = 1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a zigzag chain 1D coordination network, which is further extended into a 3D supramolecular architecture via O–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 3D open framework based on a tricadmium(II) subunit, generating a trinodal 4,4,6-connected net with the 4,4,6T24 topology defined by the point symbol of(44·62)3(46·69)2. Thermal stability and luminescent properties of both compounds were studied and discussed.     

Temperature-dependent Syntheses of Two Manganese(Ⅱ) Coordination Compounds Based on an Ether-bridged Tetracarbolylic Acid

0D dinuclear manganese(Ⅱ) coordination compound and 1 D chain manganese(Ⅱ) coordination polymer, namely [Mn_2(μ-L)(phen)4]·4 H_2 O(1) and {[Mn_2(μ5-L)(phen)_2]·H_2O}n(2), have been constructed hydrothermally using H4 L(H4 L = 2,3,3',4'-diphenyl ether tetracarboxylic acid), phen(phen = 1,10-phenanthroline), and manganese chloride at 120 and 160℃, respectively. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses(TGA), and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that two compounds crystallize in the triclinic or monoclinic system, space group P1 or P2_1/c. Compound 1 discloses a discrete dimeric structure, which is assembled into a 3 D supramolecular framework through O–H···O hydrogen bond. Compound 2 has a chain structure. Structural differences between compounds 1 and 2 are attributed to the different reaction temperature. Magnetic studies for compound 2 demonstrate an antiferromagnetic coupling between the adjacent Mn(Ⅱ) centers.     

Syntheses,Crystal Structures,and Magnetic Properties of the Cobalt(Ⅱ) and Nickel(Ⅱ) Coordination Polymers Constructed from 5-Halonicotinate and 2,2ˊ-Biimidazole

Two coordination polymers, namely [Co(5-Clnic)2(H2biim)]n 1 and {[Ni(5-Clnic)(Hbiim)]·H2O}n 2(5-Clnic H = 5-halonicotinic acid, H2 biim = 2,2ˊ-biimidazole), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a 1D chain coordination network, which is further extended into a 3D supramolecular architecture via N–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 1D chain structure based on the hexanuclear macrocycles. The adjacent 1D chains are held together into a 3D supramolecular framework via N–H···O and O–H···O hydrogen bonding interactions. Thermal stability and magnetic properties of both compounds were studied and discussed.     

Syntheses,Crystal Structures and Catalytic Properties of Copper(Ⅱ) and Cobalt(Ⅱ) Complexes Containing 5,6-Dimethylbenzimidazole

Two new complexes, [Cu(DMB)2(NAA)2](1) and [Co(DMB)2(NAA)2](2)(DMB = 5,6-dimethylbenzimidazole, HNNA = 1-naphthylacetic acid), were hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, TGA, PXRD and single-crystal X-ray diffraction analysis. The coordination geometry of the metal centers is a perfect square plane for 1 and a distorted tetrahedron for 2. In compound 1, the mononuclear units are linked by N–H···O hydrogen bonds to form a 1D chain structure, while mononuclear motifs of 2 are extended via N–H···O hydrogen bonding and π-π stacking interactions into a 2D supramolecular layer. The remarkable catalytic properties of the two complexes for the degradation of Congo red dye have been found.     

Synthesis and Crystal Structure of a New Threedimensional Thiocyanate Supramolecular Compound [Cd（phen）（NCS）（SCN）]n

The compound [Cd（phen）（NCS）（SCN）]n（phen = 1,10-phenanthroline） was synthe- sized under hydrothermal conditions and characterized by IR and single-crystal X-ray diffraction. The complex is of monoclinic, space group C2/c with a = 14.607（3）, b = 10.505（2）, c = 10.631（2）A,β = 115.14（3）^o, V = 1476.8（5）A^3, C14H8CdN4S2, Mr = 408.76, Z = 4, F（000） = 800, μ = 1.757 mm^-1 and Dc = 1.839 g/cm^3. The final R = 0.0409 and wR = 0.0811 for 1367 observed reflections （I 〉 2σ（I））. In the title compound, each cadmium atom is six-coordinated and connected with two adjacent metal ions by two NCS bridges, creating a zigzag chain. The neighboring chains are linked to each other by the weak van der Waals＇ S…S interactions and π…π interactions to form a new three-dimensional supramolecular framework.     

Novel 3-D Supramolecular Architectures Constructed from Zn^2＋ ions, Oxybis（4-benzoate） and Di（2-pyridyl）amine Ligands

Using the V-shaped oba dianions as bridging ligands and dpa molecules as terminal ligands, a new 1D helical coordination-polymeric chain, [Zn（oba）（dpa）]n [oba=oxybis（4-benzoate）, dpa=di（2-pyridyl）amine], was synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, UV-Vis and IR spectra, and TGA analysis. X-ray structural analysis revealed that, oba and dpa ligands played an important role in the self-assembly of the helical chains by providing potential supramolecular recognition sites for π-π aromatic stacking and hydrogen-bond interactions, resulting in the self-assembly of the （4,4） networks to give a 3-D supramolecular framework. The photoluminescence properties of the title compound were also investigated, showing intense blue photoluminescence properties at room temperature.     

New Inorganic-organic Hybrid Compound Containing One Dimensional Keggin Polyoxometalate[SiW11O39Co]6- Chains:Preparation,Characterization and Application in Chemically Bulk-modified Electrode

A new inorganic-organic hybrid compound based on polyoxometalate and organic ligand formulated as （H2bpp）3[SiWlIO39Co]-2H20（1）[bpp=l,3-bis（4-pyridyl）propane] was hydrothermally synthesized and structurally characterized by elemental analysis, single-crystal X-ray diffraction, IR, TG, and cyclic voltammetry. Single-crystal X-ray diffraction analysis reveals that compound 1 consists of interesting cobalt-monosubstituted POMs one dimensional chain together with protonated bpp ligands. Additionally, the polyoxoanions combined with the discrete organic substrates by hydrogen bond interactions to afford a supramolecular 3D network structure. The hybrid compound 1 was used as a bulk modifier to fabricate a three-dimensional chemically modified carbon paste electrode（1-CPE） by direct mixing. The electrochemical behavior and electrocatalysis of 1-CPE were studied in detail. The results indicate that 1-CPE has good electrocatalytic activities toward the reduction of nitrite or bromate in 1 mol/L 1-12SO4 aqueous solution. 1-CPE shows remarkable stability that can be ascribed to the insolubility of compound 1 and the supramolecular interactions existed between 1D POM anion chains and organic ligand bpp, which is very important for practical applications in electrode modification.     

A New Manganese(Ⅱ) Coordination Compound Constructed by 1,10-Phenanthroline Derivative and Chlorine Anions: Synthesis,Crystal Structure and Theoretical Calculation

The new manganese(Ⅱ) coordination compound, [Mn(Cl)_2(L)_2](1, L = 11-fluorodipyrido[3,2-a:2?,3?-c]phenazine), has been achieved under hydrothermal conditions. The structure of compound 1 was determined by single-crystal X-ray diffraction. 1 crystallizes in monoclinic system, space group C2/c with a = 8.419(2), b = 12.286(2), c = 28.451(6) ?, β = 95.889(3)°, V =2927.5(10) ?~3, Z = 4, C_(36) H_(16) MnF_2 Cl_2 N_8, M_r = 724.41, D_c = 1.644 g/cm~3, F(000) = 1460, μ(Mo Ka)= 0.691 mm~(-1), R = 0.0445 and wR = 0.0982. Adjacent compounds are stacked by one type of π-πinteraction among L ligands to generate a 1D supramolecular chain. Further, the 1D supramolecular chains are stacked by another type of π-π interaction among L ligands to give a 2D supramolecular layer. Moreover, the C-F···π interactions between the carbon atom of the L ligand and the pyrazine ring of the adjacent L ligand further stabilize the supramolecular layer of 1. In addition, natural bond orbital(NBO) analysis has been calculated by the B3LYP/LANL2DZ method, which shows obvious covalent interaction between the coordinated atoms and Mn(Ⅱ) ion.     

Hydrothermal Syntheses,Crystal Structures and Fluorescence of a Copper(I) Polymer and a Salt with H_2SO_4 Based on a Pyrimidine Building Block

Based on the building block of 2-phenyl-4,6-di(pyridin-2-yl)pyrimidine(L = C20H14N4), a Cu(I) polymer [(Cu C20H14N4)(Cu Cl2)]∞ and a salt with H2SO4 [(C20H16N4)(HSO4)2] have been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction. In the Cu(I) polymer, although the central metal ions of Cu(I) directly coordinate with the building block L, they still do not assembly expected grid-type complexes and there exists a one-dimensional chain constructed through coordinate bonds. In the salt, hydrogen bonds along with two kinds of π···π supramoleuclar interactions fabricate two-dimensional(2D) networks which further generate a 3D supramolecular architecture via interlayer π···π interactions. Fluorescent spectra show that the L emits blue fluorescence and its Cu(I) polymer and salt decrease the fluorescent intensity.     

Layered manganese 4-phosphonoisophthalates （4-piH4） embedding Mn-O chains with metamagnetism in Mn3（4-piH）2（H2O）3·H2O

Two manganese phosphonates Mn3(4-piH)2(H2O)3·H2O (1) and Mn5(4-piH)2(4-piH2)2(phen)2(H2O)4 (2) (4-piH4 = 4-phosphonoisophthalic acid, phen = 1,10-phenanthroline) have been synthesized under hydrothermal conditions in the presence of organic co-ligand. Both compounds exhibit layer structures but with different topologies. In compound 1, a complicated "ladder-like" chain of {Mn3O3}O2 which contains three- and six-member rings made up of triangular shaped {Mn3O3} trimers is found. The chains are linked by the PO3C groups to form an inorganic layer. The phenyl and protonated carboxylate groups are pendent between the layers with extensive hydrogen bonds. In compound 2, tetramers of {Mn4O6} are connected by the {MnO6} octahedra through corner-sharing to form an infinite chain, which is further bridged by 4-piH3- ligands into a thick hybrid layer. Magnetic measurements reveal that antiferromagnetic interactions are dominant in both compounds. Metamag- netism is observed in compound 1 at low temperature, while no long range ordering is found in compound 2 down to 1.8 K.     

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.     

Two New Mn(Ⅱ)/Co(Ⅱ) Complexes Assembled by 2,5-Dihydroxy-1,4-benzenedicarboxylic Acid and Phenanthroline or Derivative

Two new complexes [Mn(DHTA)(PLQ)]n(1) and{[Co2(DHTA)(phen)2(H2 O)6]· DHTA}n(2)(H2 DHTA = 2,5-dihydroxy-1,4-benzenedicarboxylic acid, PLQ = 1,10-phenanthroline-5,6-quinone, phen = 1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, fluorescence spectrum, single-crystal and power X-ray diffraction. Complex 1 exhibits a two-dimensional(2 D) network, which was stabilized through O–H···O hydrogen bonding interactions. Complex 2 shows a zero-dimensional structure, which was further extended into a three-dimensional supramolecular structure through O–H···O hydrogen bonds and π-π interactions.     

Syntheses, Structures and Luminescent Property of Two Supramolecular Complexes Containing N-P-Acetamidobenzenesulfonyl-glycine Acid Ligand

Making use of N-P-acetamidobenzenesulfonyl-glycine acid （abbreviated as abglyH2）,two transitional metal complexes [Zn（abglyH）（phen）2]ClO4·H2O （1） and Co（abglyH）2（bipy）2（H2O）2 （2） （phen = 1,10-phenanthroline,bipy = 4,4＇-bipyridine） have been synthesized under mild conditions and characterized by IR,elemental analysis and X-ray diffraction analysis. Complex 1 is a monomeric compound which is further assembled by intermolecular hydrogen bonds and π-π interaction into a 2-D supramolecular network. Complex 2 is also a monomeric compound and further connected by intermolecular hydrogen bonds to form a 2-D supramolecular network. Fluorescent analysis shows that complex 1 has an emissive maximum at 364 nm in the solution state at room temperature.     

Crystal Structures and Luminescent Properties of Three Coordination Polymers Based on 2,5-Furandicarboxylic Acid Ligand and 1,10-Phenanthroline

Three new coordination polymers,namely [Zn(FDA)(phen)(H_2O)·H_2O]_n(1),[Cd(HFDA)(phen)2(NO3)](2) and [Cd(FDA)(phen)]n(3)(H_2FDA = 2,5-furandicarboxylic acid,phen = 1,10-phenanthroline) have been synthesized by the solvothermal method and characterized by elemental analysis,IR,powder X-ray diffraction,thermogravimetric analysis and X-ray single-crystal diffraction analysis.For 1,the neighboring Zn~(2+) ions are bridged by FDA2-as linkers to form one-dimensional(1D) chains,and phen ligands are as the terminal ligands.Furthermore,the 1D chains are packed into a three-dimensional(3D) supramolecular structure through hydrogen bonds and π-π interactions.For 2,the H_2FDA ligand is partial deprotonation,which is a rare phenomenon among other coordination polymers based on H_2FDA.Under the synergetic effect of phen ligands and the partial deprotonation of H_2FDA,the structure of 2 is discrete.For 3,the Cd~(2+) ions are linked by two carboxylates of FDA2-ligand to give rise to 1 D zig-zag chains,and phen ligands chelate the Cd~(2+) ions like 1.In addition,solid-state luminescent spectra of three coordination polymers were also studied at room temperature.     

Syntheses,Crystal Structures,and Magnetic Properties of Mn(Ⅱ) and Co(Ⅱ) Coordination Polymers Constructed from Pyridine-tricarboxylate Ligand

Two coordination polymers, namely {[Mn(HL_1)(phen)]·4H_2O}_n(1) and [Co_2(HL_2)_2(H_2O)_2]_n(2) have been constructed hydrothermally using H_3L_1 and H_3L_2(H_3L_1 = 2-(5-carboxypyridin-2-yl)terephthalic acid, H_3L_2 = 2-(4-carboxypyridin-3-yl)terephthalic acid), phen, MnCl_2×4H_2O and CoCl_2×6H_2O. The products were isolated as stable crystalline solids and were characterized by IR spectroscopy, elemental, thermogravimetric(TGA), powder(PXRD) and single-crystal X-ray diffraction analyses. Compound 1 features a 3D framework structure, which was topologically classified as a trinodal 4,6,6-connected net with the unique topology defined by the point symbol of(3~(10).5.6~4)4(3~(10).6.7~4)2(5.6~2.8~2.9). Compound 2 possesses a 2D metal-organic layer, which was topologically classified as a binodal 4,4-connected layer defined by the point symbol of(4~3.6~2.8). The layers are further extended into a 3D supramolecular framework via hydrogen bonds. The magnetic properties for both compounds were also investigated, indicating antiferromagnetic interactions between the adjacent metal ions.     

Syntheses,Crystal Structures,SHG Response and Purple Luminescent Property of Tetra(isothiocyanate) Mn(Ⅱ) and Substituted Benzyl Triphenylphosphonium Cations

Researches on multifunctional molecular materials with both nonlinear optical activity and fluorescence properties have received much interest in molecular chemistry since they have wide application prospects. Here a novel ionic compound 2(BPP)~+·[Mn(NCS)_4]~(2-)(1) was synthesized via the assembly of benzyltriphenylphosphorus chloride, isothiocyanate and manganese chloride, which displays both strong SHG response and purple luminescence. Compound 1 belongs to monoclinic system and crystallizes in Cc space group. X-ray single-crystal diffraction analysis shows that Mn~(2+) ions are tetra-coordinated with N atoms of four NCS-ions through forming a distorted tetrahedral configuration. The anion Mn(NCS)_4~(2-) forms a 1D chain structure through strong S···S interaction. At the same time, there are abundant C–H···S and π···π interactions, which further accumulate into a three-dimensional supramolecular structure. Solid-state fluorescence studies show that the complex 1 has strong purple fluorescence with emission wavelength of 396 nm under excitation wavelength 248 nm. In particular, the second harmonic generation(SHG) measurements show that compound 1 has nonlinear optical activity and its SHG response is 2.25 times that of standard potassium dihydrogen phosphate(KDP). This multifunctional molecular material with SHG response and purple fluorescence is of great significance for the development of new metal organic complexes with potential application prospects.     

Syntheses,Crystal Structures and Magnetic Properties of Ni(Ⅱ) and Mn(Ⅱ) Coordination Polymers Constructed from 5-(2'-Carboxylphenyl) Nicotate and 2,2'-Biimidazole

Two coordination polymers, namely {[Ni(cpna)(H2biim)(H2O)]·H2O}n(1) and {[Mn(cpna)(H2biim)]·H2O}n(2)(H2cpna = 5-(2'-carboxylphenyl) nicotic acid, H2biim = 2,2'-biimidazole),have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. Compound 1 exhibits a one- dimensional(1D) step-like chain structure, which further builds a three-dimensional(3D) supramolecular architecture via O–H···O and N–H···O hydrogen-bonding and π-π stacking interactions. Compound 2 possesses a one-dimensional(1D) double chain structure, which is further assembled into a 3D supramolecular framework by N–H···O hydrogen bonding and π-π stacking interactions. Magnetic susceptibility measurement indicates that compound 1 shows a weak antiferromagnetic coupling between the nearest Ni(II) centers, with g = 2.11 and J = –1.87 cm–1.     

Structure and Photochemical Properties of a Chiral Cd Coordination Polymer Based on 4,4'-(Hexafluoroisopropylidene) Bis(benzoic acid) and 1,3-Di(pyridineyl)benzene

One new chiral metal-organic coordination polymer,[Cd_2(dpb)(H_2hfipbb)_2]_n,was obtained under hydrothermal conditions of 1,3-di(pyridineyl)benzene(dpb) and 4,4'-(hexafluoroisopropylidene)bis(benzoic acid)(H_2hfipbb). The title compound reveals a three-dimensional(3D) framework with two types of helical chains [Cd(COO)]n,which are linked each other to further form a double helical chain [Cd_2(COO)_2]_n by sharing the same Cd(Ⅱ) ions. The dpb connects the double helical chains to generate a 3D framework. These unique structures were studied by single-crystal X-ray and other spectroscopy techniques. In addition,the luminescent,fluorescence lifetime and second harmonic generation efficiency properties in the solid state have been studied.