Syntheses,Crystal Structures and Antibacterial Activities of Cobalt(Ⅱ) and Manganese(Ⅱ) Complexes with Schiff Base Ligand Derived from Tryptamine

Two new mononuclear complexes, namely [Co(L)_2](1) and [Mn(L)_2](2)(HL = N-(3-methylsalicylidene)tryptamine), have been synthesized by the reactions of the ligand with cobalt acetate or manganese acetate in anhydrous ethanol. The crystal structures of the complexes were characterized by IR spectrum, elemental analysis, PXRD and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group C2/c, with a = 23.146(2), b = 9.4864(10), c = 13.9261(15) ?, β = 102.898(2)°, V = 2980.6(5) ?3, Z = 4, Dc = 1.367 g/cm3, F(000) = 1284 and μ = 0.616 mm-1. Complex 2 crystallizes in monoclinic, space group P21/n, with a = 14.807(11), b = 13.118(10), c = 16.663(13) ?, β = 111.237(14)°, V = 3017(4) ?3, Z = 4, Dc = 1.342 g/cm~3, F(000) = 1276 and μ = 0.477 mm-1. The units of complex 1 are linked by intermolecular N–H···π hydrogen bonds into infinite 1D chains, which are further extended into a 3D supramolecular structure by a series of π···π stacking interactions. The units of complex 2 are linked by intermolecular N–H···π hydrogen bonds and C–H···π hydrogen bonds into an infinite 3D supramolecular structure. Meanwhile, the antibacterial activities of the ligand and its complexes have been tested against four kinds of bacteria. The results show that the three compounds all have excellent antibacterial activities and that 1 and 2 possess stronger inhibiting effects against the bacteria than the Schiff base.     

Two New Copper(Ⅱ) Complexes with p-Cyanobenzoic Acid: Synthesis,Crystal Structures and Properties

The complexes of [Cu(bpy)(H2O)(CBA)2]n 1 and [Cu(phen)(H2O)(CBA)2]·H2O 2 based on p-cyanobenzoic acid(HCBA) have been synthesized in aqueous ethanolic solution at room temperature. The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in orthorhombic and complex 2 is of triclinic system. The results indicate the complex 1 shows a 1D chain structure bridged by two carboxylic oxygen atoms from CBA–, and complex 2 is a mononuclear structure. Through intermolecular hydrogen bonding and π...π stacking interactions, the complexes are assembled into supramolecular structures. Complex 1 has been characterized by magnetic measurements. The magnetic measurement indicates that weak ferromagnetic interaction(zJ= 0.038(5)) between the Cu2+ ions is dominant in the structure. The IR spectrum and results of thermal and elemental analyses are also presented.     

Two Metal Ion-controlled Zn(Ⅱ)/Cd(Ⅱ) Coordination Polymers Based on 1,3,5-Benzenetricarboxylic Acid

Two new coordination polymers {[Zn(Hbtc)(bpyb)]·H_2O}n(1) and {[Cd(Hbtc)-(bpyb)_(1.5)]·0.5 bpyb}_n(2)(H_3btc = 1,3,5-benzenetricarboxylic acid, bpyb = 1,4-bis(4-pyridyl)benzene) have been synthesized under hydrothermal conditions. The two compounds were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Compound 1 displays a 2-fold interpenetrating 3D supramolecular architecture through O–H···N/O hydrogen bonds and π-π stacking interactions. Compound 2 exhibits a 2D→3D polycatenated structure, which is further stabilized by O–H···N hydrogen bonds. The results indicate that the metal ion has significant effects on the formation and structure of the resulted coordination polymers. Furthermore, thermal stability and photoluminescent properties of 1 and 2 are also discussed in detail.     

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.     

Trimer formation of 6-methyl-1,3,5-triazine-2,4-diamine in salt with organic and inorganic acids:analysis of supramolecular architecture

Although the numbers of co-crystals,salts,polymorphs,hydrates,and solvates are growing steadily,trimers that contain both inorganic and organic acids are still very rare in the Cambridge Structural Database(CSD).When 3,5-dihydroxybenzoic acid was crystallized readily with 6-methyl-1,3,5-triazine-2,4-diamine in a 4:3 ratio of ethanol and water by adding a few drops of nitric acid upon slow evaporation in ambient conditions,6-methyl-1,3,5-triazine-2,4-diamine and 3,5-dihydroxybenzoic acid with the nitric acid form of 1:1:1 an inorganic-organic salt formulated as[(C4H8N5+)·(NO3-)·(C7H6O4)].The supramolecular architecture,which is quite elegant and simple,appeared as stacking of a 3D network in adduct.Proton transfer from the HNO3to 6-methyl-1,3,5-triazine-2,4-diamine N acceptor(triazine N)occurred in the organic salt and led to the ionic heterosynthon in the structure.Cooperation among the–COOH,–OH,NO3–,and–NH–functional groups for the observed hydrogen bond synthon was examined in the structure.In adduct,recognition among the constituents is established through N–H···O,O–H···N,and O–H···O hydrogen bonds.The agomelatine molecules are linked through the intermolecular hydrogen bonding interactions(O–H···O)to form a 1D chain.In addition,the nitric acid anions and base cations act as donors and acceptors of hydrogen bonds and interlink,almost to co-planarity,the hydrogen-bonded chains through interchain N–H···O,O–H···N,as well as O–H···O interactions into a 2D sheet structure.Persistent N–H···O interactions were found to play an important role in the formation of the final 3D array.The salt was characterized by elemental analysis,IR,thermogravimetric analysis,and singlecrystal X-ray diffraction,to better understand how intermolecular interactions influence its supramolecular assembly.     

Crystal Structures and Theoretical Calculation of Zn（Ⅱ） and Cu（Ⅱ） Supramolecular Complexes Based on Macrocyclic Triamine Ligand 1,4,7-Triazacyclodecane （tacd）

Two supramolecular complexes [Zn（tacd）2]（C6H8O4）·6H2O（1） and [Cu（tacd）2]Cl2·4H2O（2） were synthesized and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction analysis. The crystal structure showed that the metal ions in complexes 1 and 2 had similar coordination circumstance. But for the complex 2, it formed a novel two-dimensional supramolecular network with 12-membered rings and four-membered rings via hydrogen bond interaction. The thermal gravimetric analyses indicated that the two complexes had similar steps of weight-loss. On the basis of experiment, the two complexes were calculated by DFT-B3LYP/6-31G（d） in Gaussian 03. The results of calculation are in good agreement with the experiment.     

Two Cd(Ⅱ) Coordination Polymers Based on a Flexible Tricarboxylate Ligand: Syntheses,Structures, and Photoluminescence and Catalytic Properties

Studies on the synthesis and design of coordination polymers(CPs) with flexible ligands are of great interest owing to their dynamic structures and promising applications. The title coordination polymers, {[Cd·(HTTTA)·(phen)]·2H_2 O}n(1) and [Cd·(HTTTA)·(phen)]n(2)(H3 TTTA = 2,2',2'-[1,3,5-triazine-2,4,6-triyltris(thio)] tris-acetic acid, phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, IR, powder XRD and single-crystal X-ray diffraction. Complex 1 consists of one CdII ion, one HTTTA2-ligand and one phen co-ligand. The Cd(Ⅱ) metal clusters were bridged by the tridentate HTTTA2-ligands into infinite 1D chains, which are further connected into the 3D architecture by abundant hydrogen bonds. In 2, three carboxyl groups of HTTTA2-ligand show different coordination directions because of the C–S–C flexible bond angle, which leads to different 1D chains of 2. The strong π-π stacking interaction and four C–H···O hydrogen bonds connect the 1D chains into a 3D framework. The solid-state photoluminescence and catalytic properties were studied as well.     

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 and Crystal Structure of Diaquabis{2,4-dibromo-6-[(2-ethylaminoethylimino)methyl]-phenolato}nickel(Ⅱ) Dinitrate Diacetonitrile

The title mononuclear Schiff base nickel(Ⅱ) complex [Ni(C11H14Br2N2O)2(H2O)2]· 2NO3·2C2H3N was prepared and characterized by elemental analysis,IR spectrum,and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system,space group P21/n with a=15.534(2),b=7.647(1),c=16.435(2),β=103.252(2)o,V=1900.3(4)3,Z=2,Dc=1.750 g/cm3,Mr=1000.99,λ(MoKα)=0.71073,μ=4.776 mm-1,F(000)=996,the final R=0.0368 and wR=0.0724. A total of 3988 unique reflections were collected,of which 2764 with I > 2σ(I) were observed. The complex consists of a mononuclear [Ni(C11H14Br2N2O)2(H2O)2]2+ cation,two nitrate anions and two acetonitrile molecules. The Ni atom,lying on the inversion centre,is six-coordinated by two Schiff bases and two water molecules to assume an octahedral coordination geometry. The molecules in the crystal are linked through intermolecular hydrogen bonds of N–H…O,N–H…Br,O–H…O,O–H…N and C–H…O to form layers.     

Synthesis,Structure and Catalytic Activity of a Manganese(Ⅲ) Complex Based on 2-(2-Hydroxyphenyl)-5,6-dichlorobenzimidazole Ligands

A new ligand, 2-(2-hydroxyphenyl)-5,6-dichlorobenzimidazole, H2pbmCl2(1), and a novel MnIII complex, [MnIII(HpbmCl2)(pbmCl2)(DMF)2](2),(DMF = N,N-dimethylformamide), have been synthesized and characterized. The crystal of compound 1(C13H8Cl2N2O, Mr = 279.12) belongs to the monoclinic system, space group P21 with a = 3.770(5), b = 25.20(3), c = 5.865(7) , = 92.727(17)o, V = 556.6(12) 3, Z = 2, Dc = 1.665 g/cm3, S = 1.137, μ= 0.568 mm-1, F(000) = 284, the final R = 0.0876 and wR = 0.2334 for 1848 independent reflections. The molecule is planar due to the presence of a strong intramolecular hydrogen bond between O–H group of phenol and N atom of imidazole. H2pbmCl2(1) molecules are arranged into a one-dimensional linear chain through intermolecular hydrogen bonds(N–H···O and C–H···Cl). The crystal of complex 2(C32H27Cl4MnN6O4, Mr = 756.34) belongs to the monoclinic system, space group P21/c with a = 19.043(10), b = 10.808(5), c = 18.704(11), = 115.540(6)o, V = 3473(3) 3, Z = 4, Dc = 1.446 g/cm3, S = 1.3, μ = 0.733 mm-1, F(000) = 1544, the final R = 0.1219 and wR = 0.2681 for 7811 independent reflections. The Mn ion adopts a distorted octahedral geometry coordinated by two deprotonated H2pbmCl2 ligands and two DMF molecules. The [MnIII(HpbmCl2)(pbmCl2)(DMF)2] molecules are arranged into a three-dimensional structure through hydrogen bonds(N–H···N, C–H···N and C–H···Cl) and weak π···πinteractions. The activity measurements suggest that complex 2 is able to serve as a catalyst for H2O2 disproportionation reaction to form O2 in neutral water solution.     

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.     

Two Novel Mercury(Ⅱ) and Copper(Ⅱ) Complexes Based on(5-Chloro-quinolin-8-yloxy)acetic Acid

Two novel mononuclear complexes with 5-chloro-8-(methoxycarbonylmethoxy)quinoline ligand(L), namely, HgLBr_2 1 and CuL_2Cl_2 2, have been prepared by solvothermal reaction of(5-chloro-quinolin-8-yloxy)acetic acid with HgBr_2 and CuCl_2, respectively. Their structures were characterized by IR, elemental analysis, UV-Vis-NIR spectra, TG and single-crystal X-ray diffraction analysis. Interestingly,(5-chloro-quinolin-8-yloxy)acetic acid is changed as 5-chloro-8-(methoxycarbonylmethoxy)quinoline ligand(L) in complexes 1 and 2. Crystal data for 1: C12H10Br2 Cl Hg NO3, Mr = 612.07, triclinic, space group P1 with a = 8.5983(7), b = 9.7726(6), c = 10.1549(6) ?, α = 66.355(6), β = 77.067(8), γ = 78.803(8)°, V = 756.6(9) ?3, Z = 2, Dc = 2.687 g/cm3, F(000) = 560, μ = 15.633 mm-1, R = 0.0351 and w R = 0.0504. Crystal data for 2: C24H20Cl4 Cu N2O6, Mr = 637.76, triclinic, space group P1 with a = 10.5324(9), b = 11.2377(16), c = 12.0143(12) ?, α = 83.413(11), β = 64.475(9), γ = 83.144(11)°, V = 1270.9(2) ?3, Z = 2, Dc = 1.667 g/cm3, F(000) = 646, μ = 1.324 mm-1, R = 0.0408 and w R = 0.0922. In 1, the HgII centre is a distorted trigonal planar geometry comprised of two Br atoms and one quinoline N atom of L. Intermolecular π-π, C–H···π stacking interactions and intermolecular C–H···Br hydrogen bonds are observed in the molecular packing of 1. In complex 2, each CuII center has a distorted octahedral geometry comprised of two chloride ions, two quinoline N atoms and two O atoms of two L ligands. Intermolecular C–H···Cl hydrogen bonds exist in the molecular packing of 2. The fluorescence emission peak of complexes 1 and 2 appears near 406 and 410 nm, respectively. Optical diffuse-reflection spectral results suggest complex 1 has the property of semiconductor.     

Syntheses,Structures,and Properties of Two New Coordination Polymers Based on Tetracarboxylate and 2,2′-Bipyridine Mixed Ligands

Two new coordination polymers {[Zn2L1(2,2'-bpy)2(H2O)2]·4H2O}n(1) and [Zn2L2(2,2'-bpy)2(H2O)2]n(2)(H4L1 = terphenyl-2,2',4,4'-tetracarboxylic acid, H4L2 = quarterphenyl-2,2',4,4'-tetracarboxylic acid, and 2,2'-bpy = 2,2'-bipyridine) have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction studies. Complex 1 displays 2D wavelike networks, which are further joined together through O–H···O hydrogen bonds to give a 3D supramolecular network. Complex 2 exhibits 1D ladder-like chains, and they are further joined together by π-π stacking and O–H···O hydrogen bonding interactions to form a 3D supramolecular network. The results indicate that the backbone of carboxylate ligands has significant effects on the formation and structure of the resulting functional coordination polymers. Additionally, thermal stability and photoluminescent properties of 1 and 2 are also investigated in detail.     

A New Cadmium(Ⅱ) Coordination Polymer Extended through Hydrogen Bonds and π-π Stacking Interactions: Synthesis and Photoluminescence Property

A new coordination polymer, {[Cd(OPY)_2(tdc)(H_2O)]·H2 O}n(OPY = 4,4?-(oxybis(4,1-phenylene))dipyridine, H2 tdc = thiophene-2,5-dicarboxylic acid), has been synthesized hydrothermally based on a V-shaped ligand OPY. The structure was fully characterized by elemental analysis, FT-IR spectroscopy, and X-ray single-crystal diffraction analysis. In1, two OPY ligands and one water molecule acted as terminal ligands coordinating to Cd~(2+) cation to form [Cd(OPY)_2 H_2O]~(2+) units, which are then linked by tdc2-ligands to generate a one-dimensional chain. Every two adjacent chains linked by extensive O–H···O hydrogen bonds constitute one-dimensional double-chains, and such chains are extended into two-dimensional layers via O–H···N hydrogen bonds. These layers are further connected to form a three-dimensional supramolecular architecture via π-π stacking interactions. In addition, the thermal stability and solid state fluorescence property of 1 were also investigated.     

Synthesis,Crystal Structure and DNA-Binding Property of a Mn(Ⅱ) Complex Based on 5-(Tri-fluoromethyl)pyridine-2-carboxylic Acid

A new complex Mn(Htpc)_2(H_2O)_2(1, Htpc = 5-(trifluoromethyl)pyridine-2-carboxylic acid) has been synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. 1 belongs to triclinic system, space group P■ with a = 5.0885(10), b = 6.5574(13), c = 14.016(3) ?, β = 90.67(3)o, V = 436.34(17) ?~3, Z = 1, D_c = 1.793 g·cm~(-3), μ = 0.855 mm~(-1), Mr = 471.18, F(000) = 235, the final R = 0.0454 and wR = 0.1134 for 1998 observed reflections with I 2σ(I). The Mn(Ⅱ) ion is coordinated by two N and two O atoms from two Htpc as well as two O atoms from two coordinated water molecules, forming a 0D motif with distorted octahedral coordinate geometry. The adjacent 0D units are linked into 1D chains through hydrogen bond O(1W)–H(1 WB)···O(2), and via the O(1 W)–H(1 WA)···O(1) hydrogen bond the neighboring 1D chains are connected into a 2D supramolecular layer. Moreover, the interactions between the ligand and its complex with CT-DNA were studied by EtBr fluorescence probe, which suggested that these compounds bind to CT-DNA through an intercalation mode. The binding constants were 0.41 and 0.64 for Htpc and complex 1, respectively. It indicates that the interaction between complex 1 and CT-DNA is stronger than Htpc.     

Synthesis,Structure and DFT Calculations of a Novel Copper(Ⅱ) Complex Based on Tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate

A novel copper(Ⅱ) complex with tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate(ampy) was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper(II) complex with ampy, [Cu(ampy)Cl2](1), was formed irrespective of the metal-to-ligand molar ratios([Cu2+]:[ampy] = 0.5:1, 1:1, and 2:1) as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343(2), b = 18.928(3), c = 20.058(4) ?, V = 4686.1(14) ?3, Z = 8, Dc = 1.3349(4) g/cm~3, F(000) = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I 2σ(I). X-ray diffraction analysis reveals that the central copper(II) ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H···Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory(DFT/B3LYP) method with the basis sets(6-31+G(d,p) for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively). The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital(NBO) analysis and frontier molecular orbitals(FMOs) analysis were investigated at the same level.     

Syntheses,Crystal Structures and Magnetic Properties of Two New Low-dimensional Manganese (Ⅱ) Coordination Compounds

Two new low-dimensional Mn(Ⅱ) coordination compounds of Mn(H_2pimdc)_2(phen)(compound 1) and [Mn(Hpimdc)(phen)]n·nH_2O(compound 2) were synthesized, where H_3pimdc is a 2-propyl-imidazole-4,5-dicarboxylic acid and phen is 1,10-phenanthroline. Both compounds were thoroughly analyzed by X-ray single-crystal diffraction, element analysis, IR spectra, PXRD and thermal analysis. X-ray single-crystal diffraction analyses indicate that the phen ligands terminate metal ions on two sides to prevent the linkage between the neighboring metal ions into a higher dimensional structure in compounds 1 and 2. Compound 1 is constructed from mononuclear molecules which form the 1D helical supramolecular chain by N–H···O hydrogen bonds. In compound 2, Hpimdc is a tetradentate bridging ligand, which binds Mn(Ⅱ) ions to generate a single-stranded right helical chain parallel to the b axis. These 1D chains are additionally coupled by H-bonds as well as π···π stacking interactions, which formed a 3D supramolecular structure. Additionally, compound 2 demonstrated temperature-dependent magnetic susceptibility and negative value of θ(equal to –9.09 K), which is indicative of weak antiferromagnetic interactions between Mn(Ⅱ) ions.     

Two Zn(Ⅱ)/Cd(Ⅱ) Metal-organic Frameworks Constructed from 1,3,5-Benzenetricarboxylic Acid and1,4-Bis(1-imidazolyl)benzene:Syntheses,Structures and Photoluminescent Properties

Two new d~(10 )metal-based metal-organic frameworks,{[Zn_3(btc)_2(bib)_2(H_2O)_2]·2H_2O}_n(1)and{[Cd_3(btc)_2(bib)_(1.5)(H_2O)_6]·6H_2O}_n(2)(btc=1,3,5-benzenetricarboxylate anion,bib=1,4-bis(1-imidazolyl)benzene)have been prepared under hydrothermal conditions by the reactions of d~(10 )metal oxides of ZnO and CdO with the aromatic polycarboxylic H_3btc and the N-heterocyclic bib.The two products were characterized by single-crystal X-ray diffraction analysis,elemental analysis,thermogravimetric analysis(TGA),and IR spectroscopy.Complexes 1 and 2 crystallize in monoclinic C2/c and triclinic P 1 space groups,respectively.1 shows a 3D framework,and the potential large voids of the 3D network lead to a 3-fold interpenetrating architecture.2 displays a 2D framework,and the adjacent 2D layers expand into a 3D supramulecular network via rich hydrogen bonds.Moreover,the luminescent properties of the two complexes are investigated in solid state.     

Structures and Properties of Two Pillared-layer Mn(Ⅱ) MOFs with 5-Ethyl-pyridine-2,3-dicarboxylate

The reaction of Mn(OAc)2·4 H2 O, 5-ethyl-pyridine-2,3-dicarboxylic acid(H2 epda) and 4,4?-bipyridine(4,4?-bipy)/4,4?-bis(imidazolyl)biphenyl)(bibp) under hydrothermal conditions produced two new manganese(Ⅱ) MOFs [Mn(epda)(4,4?-bipy)1/2](1) and [Mn(epda)(bibp)1/2](2), which were characterized by elemental analysis, infrared spectroscopy, thermogravimetric analyses, and single-crystal X-ray diffraction. The structures of complexes 1 and 2 are similar. In 1, the adjacent Mn(Ⅱ) ions are connected by epda dianion to generate a 2 D(4,4) grid layer, and such 2 D layers are further connected via bibp ligand to form another layer, forming a 2 D pillared-layer. Topologically, the Mn atoms as the node are bridged by the edpa anions and bibp ligands to form a uninodal 5-connected network topology. The magnetic properties of 1 and 2 have also been-investigated, and the exchange interctions were –1.39 and –1.05 cm1, respectively. According to the crystal structures, compounds 1 and 2 were carried out by using hybrid DFT methods at the B3 LYP/6-31 G(d) level. The DFT-BS approach was applied to study the magnetic coupling behaviors for 1 and 2. The result reveals that the calculated exchange coupling constants J were in good agreement with the experimental data.     

Syntheses,Crystal Structures and DNA-binding Properties of Cd(Ⅱ), Co(Ⅱ), Cu(Ⅱ) and Zn(Ⅱ) Complexes Containing Imidazolium Derivatives

Cd(Ⅱ), Co(Ⅱ), Cu(Ⅱ) and Zn(Ⅱ) complexes(1~4) based on 2-(2-pyridyl)benzimidazole(pbm) and 4,4'-oxybisbenzoic acid(H2odc) were synthesized. The formulas of these complexes are [Cd(pbm)(odc)2](1), [Co(pbm)(odc)2](2), [Cu(pbm)(odc)2](3) and [Zn(pbm)(odc)2](4) confirmed by single-crystal X-ray diffraction analysis, which shows that complexes 1, 2 and 4 belong to monoclinic system with space group P21/n, while complex 3 belongs to monoclinic system with space group P21/c. The binding properties of complexes 1~4 with CT-DNA are evaluated by ultraviolet spectrum, fluorescence spectra and viscosity measurements. The results indicate that complexes 1~4 have strong interaction with CT-DNA binding. These complexes exhibit an electrostatic or groove mode in respect of binding with DNA, which can effectively destroy DNA. And this binding mode may be applied to the interaction between the complexes and cancer cell DNA. Therefore, we hope to provide a theoretical and scientific basis for the research of anti-cancer drugs.