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 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 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.     

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,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 and Crystal Structure of an Unusual Dodecacoordinated Lanthanum Complex by Phenanthroline and Nitrate （phenH）_2[La（NO_3）_5（phen）]·CH_3OH

Lanthanum complex (phenH)2[La(NO3)5(phen)]·CH3OH (1, phen=phenanthroline) was synthesized and characterized by single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/c with a=20.3040(3), b=10.7091(1), c=19.0771(2), β=102.090(1)°, V=4056.07(8)3, Z=4, Dc=1.676 g/cm3, μ= 1.142 mm-1, F(000)=2056, the final R=0.0346 and wR=0.0793 for 9981 (Rint=0.0358) independent reflections. The mononuclear complex 1 consists of four parts: two phenH+ cations formed by the protonation of phen, one complex anion [La(NO3)5(phen)]2-, and one solvent methanol molecule. The complex anion contains one phen and five nitrate ligands which both chelate the center La(III) ion, adopting a distorted twelve-coordinated icosahedral geometry. The cations, anion and solvent molecule are linked together by hydrogen bonds. One of the protonated phenanthrolines (phenH+) acting as cation connects to the anion via N–H…O hydrogen bond directly, and the other one links to the anion through an intermediate solvent CH3OH via N–H…O and O–H…O hydrogen bonds. By the plentiful additional weak C–H…O intermolecular hydrogen bonds, the compound molecules construct a two-dimensional layer structure.     

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.     

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.     

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 Zn~Ⅱ Coordination Polymers with 2,2?-Oxybis(benzoic acid) and Different N,N?-Donor ligands

Two new Zn~Ⅱ coordination polymers [Zn(oba)(4,4?-bipy)]n(1) and [Zn(oba)-(bpe)_(1/2)(H_2O)]_n(2)(H_2oba = 2,2?-oxybis(benzoic acid), 4,4?-bipy = 4,4?-bipyridine, bpe = 1,2-bis(4-pyridyl)ethylene) were synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, IR spectroscopy and elemental analysis. Complex 1 shows a 3D metal-organic framework with a uninodal 4-connected 65.8 dmp network. Complex 2 features 1D ladder-shaped chains, which are further connected into a 2D stair-step network through intermolecular O–H···O hydrogen bonds.     

Synthesis,Characterization and Thermostability of a Novel Pb(Ⅱ) Coordination Polymer with Mixed Ligands

A novel mixed-ligand coordination polymer [Pb(phen)(NNDS)(H2O)]n·n H2O(1) was obtained from the reaction of 1,10-phenanthroine(phen), Pb(OAc)2 and sodium 1-nitroso-2-naphthol-3,6-disulfonate(Na2NNDS) in a mixed solvent. The complex was characterized by elemental analysis, IR and X-ray single-crystal diffraction. Crystal data for 1: monoclinic, space group P21/c, a = 11.5835(9), b = 14.6334(11), c = 13.9030(11) ?, β = 98.4180(10)o, V = 2331.3(3) ?3, Z = 4, Mr = 754.70, Dc = 2.150 mg/m3, μ = 7.483 mm-1, F(000) = 1456, the final R = 0.0430 and w R = 0.0841 for 4221 observed reflections with I 2σ(I). The Pb(II) center is coordinated by six O and two N atoms showing a distorted dodecahedron configuration. The multidentate ligand of NNDS dianion exhibits peculiar coordination mode, and the two O atoms of two sulfonate anions bridge two Pb(II) cations into a dimer, and the O atom of nitroso group links the other dimer into 2D sheets extending in the [011] plane. There exist significant π-π stacking interactions between adjacent phen and NNDS. The 3D network is formed by 2D sheets interlinked by hydrogen bonds and π-π stacking interactions. The thermostability of 1 was investigated by TG and DSC.     

A 2D Lanthanide-organic Framework Based on Inorganic Lanthanum（Ⅲ） Sulfate Skeletons：Synthesis,Structure,and Luminescence and Thermal Properties

A new lanthanum coordination polymer formulated as {[La2(pyda) 2(μ4-SO4) ·5H2O]· 2H2O}n(1,H2pyda = 2,6-pyridine-dicarboxylic acid) has been synthesized from the reaction of H2pyda with lanthanide nitrate in the presence of sulfate as a counter anion. The compound was characterized by elemental analysis,IR spectroscopy and X-ray single-crystal diffraction. It crystallizes in the orthorhombic system,space group Pna21,with a = 18.8558(19) ,b = 6.5831(7) and c = 18.7543(19) . The compound is a 2D hybrid,in which the La(Ⅲ) ions were doubly connected by the carboxylic group of pyda2-ligand to form the La(Ⅲ) dimer followed by being grafted into 1D zig-zag chains which are further connected into a 2D network containing {[La(SO4) ]+}n helical chains. The interchain hydrogen bonding and π-π stacking interactions extended the 2D networks into a 3D supramolecular edifice.     

Cd/Mn(Ⅱ) Complexes with Heterocyclic Substituted 1,2,4-Triazole Ligands:Syntheses,Crystal Structures,and Luminescence Properties

Based on a 3-(pyridine-2-yl)-4H-1,2,4-triazole ligand(Hpytr), one 2D Cd(Ⅱ) coordination polymer [Cd I(pytr)]_n(1) and one 2D Mn(Ⅱ) coordination polymer [Mn(N_3)(pytr)(H_2O)]_n(2) have been synthesized and characterized by X-ray crystallography, elemental analysis, and fluorescence spectroscopy. 1 shows a layer coordination architecture linked by pytr ligand, and the Cd(Ⅱ) centers display slightly distorted square pyramid coordination geometries. Complex 2 shows a 2D pillared-layer coordination architecture bridged by N3-and pytr, and the Mn(Ⅱ) centers display slightly distorted octahedral geometries. The luminescent properties of 1 and the PXRD and thermal stability of complexes 1 and 2 were measured briefly.     

Supramolecular Architecture from the Self-assembly of One-dimensionalCoordination Polymers and Hydrogen Bonds

The synthesis and characterization of coordination polymers have been a rapid growth area in recent years. The coordination polymers consist of 1D chains, 2D sheets or 3D networks in which metal-organic building blocks connected via coordinate and hydrogen bonds. They received considerable attention because of their versatile intriguing architectures, topologies and potential applications in materials1,2 . As rigid rod-like spacers, 4,4'-bipyridine and its analogues have been used to give r…     

Structural Diversity and Luminescent Properties of Metal-organic Frameworks Based on a Rare Sulfonate and Imidazole Co-Ligand System

Four types of luminescent properties of metal-organic frameworks(MOFs) with formulas [Cd(1,2-BIYB)2(H_2O)_2]_n·n(AQ-1,5-DAD)(1), [Cd(AQ-1,5-DAD)(1,3-BIYB)_2]_n(2), [Cd(1,3-BIYB)]n·n(AQ-1,5-DAD)·n H_2O(3), and [Zn(1,4-BIYB)_2]_n·n(AQ-1,5-DAD)2·6H_2O(4),(Na_2AQ-1,5-DAD = anthraquinone-1,5-disulfonic acid disodium, 1,2-BIYB = 1,2-bis(imidazol-1-ylmethyl)benzene, 1,3-BIYB = 1,3-bis(imidazol-1-ylmethyl)benzene, 1,4-BIYB = 1,4-bis(imidazol-1-ylmethyl)benzene) have been synthesized based on a rare sulfonate and imidazole Co-ligand system under different conditions. The structural features of four types of MOFs 1~4 are as follows: MOFs 1 show a 3D supramolecular compound in which the double one-dimensional chains are further cross-linked by hydrogen bonds. 2 exhibits a 2D network constructed by two different 1D chains. 3 features a 2D supramolecular network, in which the 1D chains and AQ-1,5-DAD are arranged alternately through hydrogen bonds. 4 posseses a 3D supramolecular structure constructed by a 2D network and one-dimensional hydrogen bonding chains. All compounds 1~4 are characterized by elemental analysis, infrared spectroscopy, and thermogravimetric analysis. The luminescence properties of 1~4 have been investigated.     

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.     

A Zn(Ⅱ) Coordination Polymer Based on a Flexible Polycarboxylate Ligand 5-(4-Hydroxypyridinium-1-ylmethyl)-isophthalic Acid: Synthesis,Structure, and Property

A Zn(Ⅱ) supramolecular coordination polymer, {[Zn_2(L)_2(m-bix)(H_2O)]·6 H_2O}n(1), with an interesting 1 D→2 D polythreading array from a flexible and angular organic aromatic polycarboxylate ligand 5-(4-hydroxypyridinium-1-ylmethyl)isophthalic acid(H2 L), and N-donor ligand 1,3-bis(imidazol-1-ylmethyl)benzene(m-bix), has been obtained under hydrothermal conditions and characterized by elemental analysis, powder X-ray diffraction(PXRD), IR, thermal gravimetric analyses(TGA) and single-crystal X-ray diffraction. In 1, the Zn(Ⅱ) center has two coordination geometries. One exhibits a trigonal bipyramidal coordination sphere, and the other is a tetrahedral geometry; L2-has two different coordination modes, with one connecting three Zn(Ⅱ) ions through two monodentate carboxylate groups and the monodentate hydroxyl group, and the other bridging two Zn(Ⅱ) ions through two carboxylate groups. The L2-anions connect the Zn(Ⅱ) centers forming an infinite 1 D tubular structure. These 1 D tubes are interconnected by the m-bix spacers to form a 2 D framework. Such 2 D layers are further assembled into a 3 D supramolecular network via hydrogen bonds. Meanwhile, the luminescent property of 1 has also been investigated in detail.     

Spacer Length Effects on the Structure of Cd(Ⅱ) Coordination Polymers with Flexible Bis(thiabendazolyl)(1) Alkane and 1,2,4,5-Benzenetetracarboxylte Ligands

The hydrothermal reactions of Cd(OAc)2·2H2O with 1,2,4,5-benzenetetracarboxylic acid(H4bta) and 1,4-bis(thiabendazolyl)butane(L1) or 1,6-bis(thiabendazolyl)hexane(L2) afforded two coordination polymers [Cd2(L1)(bta)·2H2O]n(1) and [Cd2(L2)2(H2bta)2]n(2). Complex 1 holds a rare 3D binodal(4,6)-connected framework with fsh topology. Complex 2 features an infinite meandering chain structure, which is further extended via O–H···O hydrogen bonding into a 3D supramolecular network. The thermal and fluorescence proprieties of the two complexes were investigated.     

Synthesis, Characterization and Crystal Structure Determination of a Thiocyanato Bridged One-dimensional Polymeric Complex of Cadmium(Ⅱ)

A new one-dimensional polymeric complex [Cd(SCN)2(H2O)]L (L = N,N?-bis(furan- 2-ylmethylene)hydrazine) has been synthesized and characterized by IR, UV spectra, TG-DTA technique and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, pace group P1 with a = 5.9268(8), b = 10.8678(15), c = 13.3671(19) , α = 109.295(2), β = 95.092(2), γ = 97.8580(10)°, V = 796.70(19) 3, Z = 2, C12H10CdN4O3S2, Mr = 434.76, μ = 1.648 mm–1, Dc = 1.812 g/cm3, F(000) = 428, R = 0.0308 and wR = 0.0769. The crystal structure reveals that the structure of [Cd(SCN)2(H2O)]n features di-μ-1,3-thiocyante bridges and 1D chains. The octahedrally coordinated Cd atom is surrounded by one oxygen atom from water molecule, three S atoms and two Natoms from five di-μ-1,3 thiocyanato bridges. The Cd atoms are connected by two di-μ-1,3 thiocyanato bridges with the Cd(1)…Cd(1A) separation of 4.239(1)  and Cd(1)…Cd(1B) of 5.852(1). In addition, the one-dimensional straight chain structure is further connected by multiform intermolecular N-H…O hydrogen bonds and π…π interactions to form a three-dimensional supramolecular structure.