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.     

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.     

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 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.     

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.     

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.     

A New 1D Cd(Ⅱ) Coordination Polymer Constructed by 2,2'-H_2biimidazole:[Cd(H_2biim)_2(SO_4)]_n·3nH_2O

A new 1D Cd(II) coordination polymer, [Cd(H2biim)2(SO4)]n·3n H2O(1, H2 biim = 2,2'-H2biimidazole), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 6.8405(14), b = 17.792(4), c = 14.987(3) A, β = 92.68(3), V = 1822.1(6) A3, Z = 4, C12H18 Cd N8O7S, Mr = 530.80, Dc = 1.935 g/cm3, F(000) = 1064, μ(Mo Ka) = 1.371 mm-1, R = 0.0280 and w R = 0.0617. In 1, adjacent Cd(II) atoms are bridged by sulfate anions in bidentate modes to yield a 1D chain. H2 biim ligands are located on both sides of the chain in chelating bidentate modes. Further, the H2 biim ligands from neighboring chains are paired through π-π interactions to generate a supramolecular layer, which is stabilized by the complicated N–H···O and O–H···O hydrogen bonds. In addition, thermal behavior and luminescent property of 1 have been investigated.     

Syntheses,Structures and Catalytic Properties of Two Mn(Ⅱ) and Cd(Ⅱ) Coordination Polymers through in Situ Ligand Reaction

Two coordination polymers, namely [Mn(μ-Hcpia)(bipy)(H_2O)_2]_n(1) and [Cd_3(μ_3-Hcpia)_2(μ-Hbiim)_2(μ-H_2biim)(H_2O)_2]_n(2), have been constructed hydrothermally using H_2cbia(H_2cbia = 5-(4'-cyanobenzoxy)isophthalic acid), bipy(bipy = 4,4'-bipyridine), H_2biim(H_2biim = 2,2'-biimidazole), and manganese or cadmium chlorides at 160℃. Interestingly, the H_3cpia(H_3cpia = 5-(4'-carboxylphenoxy)isophthalic acid) ligand was generated by in situ hydrolysis of cyano group in H_2cbia. 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. Both compounds crystallize in the triclinic system, space group P1. Compound 1 discloses a 1D linear chain of the 2C1 topological type. Adjacent chains are assembled into a 2D supramolecular sheet through O–H···O/N hydrogen bonds. Compound 2 features a 3D framework with a 3,4,4 T25 topology. The luminescent and catalytic properties of two compounds were investigated. Compound 1 exhibits a superior catalytic activity in the cyanosilylation at room temperature.     

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.     

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.     

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 Characterizations of Two New Zinc(Ⅱ) Coordination Polymers Constructed from 3-(1H-Pyrazol-4-yl)-5-(pyridin-2-yl)-1,2,4-triazole and Different Carboxylate Ligands

Two new zinc(Ⅱ) coordination polymers, [Zn(ph)(H2 L)·H_2O]2 n(1) and [Zn(ip)(H2 L)-(H_2O)]n(2)(H2 ph = phthalic acid, H2 ip = isophthalic acid, H2L = 3-(1 H-pyrazol-4-yl)-5-(pyridin-2-yl)-1,2,4-triazole), have been successfully synthesized via hydrothermal reaction. It has been structurally characterized by X-ray single-crystal analysis, IR spectra, fluorescence spectroscopy and thermogravimetry analysis. The single-crystal X-ray diffraction studies reveal that compounds 1 and 2 both exhibit 1D chain structures, and assemble into 2D and 3D supermolecules through hydrogen bonds or π-π interactions. Moreover, the thermal stability and luminescent properties of compounds 1 and 2 were also studied.     

Syntheses,Crystal Structures and Magnetic Properties of Cobalt(Ⅱ) and Manganese(Ⅱ) Coordination Polymers Constructed from 5-(Pyridin-4-yl)Isophthalate Ligands

Two coordination polymers, namely {[Co(L)(H2O)]·H2O}n(1) and [Mn(L)(phen)]n(2, H2L = 5-(pyridin-4-yl)isophthalic acid, phen = 1,10-phenanthroline), have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. 1 belongs to the triclinic system, space group P1 with a = 7.2188(7), b = 10.0835(8), c = 10.2069(7) ?, α = 113.713(7), β = 99.490(7), γ = 104.516(8)o, V = 628.24(9) ?3, C13H11NCoO6, Mr = 336.16, Z = 2, Dc = 1.777 Mg/m3, μ(MoKα) = 1.395 mm–1, F(000) = 342, S = 1.041, the final R = 0.0381 and wR = 0.0819 for 3744 observed reflections(I 2σ(I)) and R = 0.0448 and wR = 0.0874 for all data. 2 belongs to the monoclinic system, space group P2/c with a = 12.9185(3), b = 10.4343(2), c = 31.7650(6)?, β = 101.282(2)o, V = 4199.08(13)?3, C50H30N6Mn2O8, Mr = 952.68, Z = 4, Dc = 1.507 Mg/m3, μ(MoKα) = 5.447 mm–1, F(000) = 1944, S = 1.128, the final R = 0.1003 and wR = 0.1052 for 8247 observed reflections(I 2σ(I)) and R = 0.2595 and wR = 0.2625 for all data. Single-crystal X-ray diffraction studies show that compound 1 features a 2D sheet structure based on a dicobalt(II) subunit, which is further extended into a 3D metal-organic supramolecular framework by O–H···O hydrogen bond. Compound 2 also possesses a 2D sheet, which is held together into a 3D supramolecular architecture via C–H···O hydrogen bond and π-π stacking interactions. Magnetic studies for compound 2 show antiferromagnetic coupling between the adjacent metal centers, with J = –11.8 cm–1 and g = 2.12 for 2.     

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.     

Hydrothermal Syntheses and Crystal Structures of Six Complexes Constructed from 1,3,5-Benzenetricarboxylic Acid and 4?-(4-Pyridyl)-2,2?:6?,2??-terpyridine Mixed Ligands

Six new transition metal complexes, [Zn(HBTC)(PYTPY)]_n·n PYTPY(1), [Cu(HBTC)(PYTPY)]_n·n PYTPY(2), [Co(HBTC)(PYTPY)]_n·n DMF(3), [Mn(HBTC)(PYTPY)]_n·n DMF(4), [Cd(HBTC)(PYTPY)(H2O)]_n·2nH_2O(5), and [Co(HBTC)(PYTPY)(H_2O)_2](6),(H_3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4?-(4-pyridyl)-2,2?:6?,2??-terpyridine, DMF = N,N?-dimethylformamide), have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional(3D) supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.     

Syntheses,Structures and Properties of Three Novel La(Ⅲ)/Co(Ⅱ) Coordination Polymers Based on 5-(3-(Tetrazo-5-yl)phenyl)isophthalic Acid

Three novel complexes, namely {[La(tapipa)(4,4′-bibp)·(H_2O)_2]·H_2O}n(1), {[La-(tapipa)(H_2O)_4(OH)]·3 H_2O}n(2), [Co(tapipa)(1,4-bbib)]n(3)(tapipa = 5-(3-(tetrazo-5-yl)phenyl)isophthalic acid, 4,4′-bibp = 4,4′-bis(imidazolyl)biphenyl, and 1,4-bbib = 1,4-bis(benzimidazo-1-ly)benzene) have been synthesized under solvothermal conditions and characterized by PXRD, IR,TGA, and so on. Complex 1 presents a 2 D layer structure, which is finally packed into a 3 D supramolecular structure by means of hydrogen bonds; complexes 2 and 3 exhibit 1 D chains and 2 D wavy-type structures, respectively, which are expanded into 3 D supramolecular structures through hydrogen bonds and π-π interactions. Furthermore, the luminescence properties of complex 1 and the variable-temperature magnetic susceptibilities of 3 were investigated. Complex 1 has highly selective sensing for Fe~(3+) and Cr_2O_7~(2-) ions.     

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.     

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.     

Syntheses,Structures and Luminescent Properties of Cd(Ⅱ)/Zn(Ⅱ) Coordination Polymers Based on the Flexible 4-Substituted Bis(1,2,4-triazole) Ligand

Two new cadmium(Ⅱ) and zinc(Ⅱ) coordination polymers, {[Cd(btre)0.5-(mip)(H_2O)_2]·H_2O}n(1) and [Zn(btre)(mip)]n(2), were synthesized at room temperature condition and characterized by IR spectra, elemental analyses, single-crystal and powder X-ray diffractions(btre = 1,2-bis(1,2,4-triazol-4-yl)ethane, H2 mip = 5-methyl-1,3-benzenedicarboxylic acid). Complex 1 belongs to the triclinic system, P1 space group, with a = 8.9830(6), b = 10.0579(6), c = 10.2479(9) ?, α = 98.837(6), β = 115.975(8), γ = 106.370(6)°, V = 756.30(11) ?~3 and Z = 2; complex 2 crystallizes in monoclinic, space group P21/c, with a = 7.0332(3), b = 14.9947(7), c = 15.9689(7) ?, β = 97.1170(10)°, V = 1671.12(13) ?~3 and Z = 4. Compounds 1 and 2 based on the same N/O-donor ligands show different structures. The one-dimensional chains of 1 are further linked by hydrogen bonding and π-π interactions to yield a three-dimensional supramolecular structure. The two-dimensional(6,3) networks of 2 are further extended into a 3D framework via π-π interactions. Thermal stabilities and luminescence of 1 and 2 were investigated.     

Syntheses and Crystal Structures of a Cadmium(Ⅱ) and a Zinc(Ⅱ) Complexes with the Flexible Ligand 1-Acetic Acid-2, 2'-biimidazole

Reactions of NaAcebiim(NaAcebiim = 1-acetic acid-2, 2′-biimidazole monosodium salt) and cadmium or zinc nitrate produce two supramolecular architectures, namely, 1D [Cd(Acebiim)(NO3)(H2O)]n(1) and 0D [Zn(Acebiim)2(H2O)2]·2H2O(2) in acidic aqueous solutions. Single-crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the triclinic system, space group P1, and 2 is of monoclinic system, space group P21/n. In 1, two nitrate groups link two Cd(Ⅱ) ions forming [Cd2(NO3)2(H2O)2] as secondary building units that are interconnected by the Acebiim- ligand into an infinite ladder. In 2, the hydrogen-bonded synthon R22(16) between the N–H moieties and carboxylic acid link [Zn(Acebiim)2(H2O)2], generating a 1D-extended ribbon. Moreover, hydrogen bonds and π-π interactions further stabilize the 3D supramolecular architecture.