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 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 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 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.     

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.     

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 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.     

Detection of NO2 Based on 4-Carboxyl-4'-hydroxy Azobenzene and Its Cu(Ⅱ) Complex

<正>An organic ligand and its Cu(II) complex formulated as (C_(13)H_(10)N_2O_3)·5H_2O (H_2L·5H_2O, 1) and Cu(HL)_2(phen)·0.125H_2O (2, H2L = 4-carboxyl-4′-hydroxy azobenzene, phen = 1,10-phenanthroline) have been synthesized and structurally characterized by single-crystal X-ray diffraction. In the two compounds, H_2L and HL exhibit a trans-conformation. Complex 2 shows a mononuclear Cu(II) structure with the hydroxyl group of HL uncoordinated. Complex 2 is assembled into a three-dimensional (3D) supramolecular architecture by hydrogen bonds and π-π stacking interactions. H_2L and compound 2 can detect NO_2 via reversible and irreversible color changes, respectively. The mechanism for the color changes is 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 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.     

Synthesis and Crystal Structure of Trans-diaquabis(hexamethylenetetramine-N)bis(isothiocyanato)cobalt(Ⅱ) trans-tetraaquabis(isothiocyanato)cobalt(Ⅱ) dihydrate

1 INTRODUCTION Supramolecular compounds assembled by coordination covalent bonding or hydrogen bonding are of considerable interest due to their potential applications in developing new materials with magnetic, optical and catalytic properties[1]. One of the synthesis methods used to construct the functional compounds is that octahedral metal ion connects to polydentate ligand such as 4, 4?bipyridine, pyrazine and so on to form multi-dimensional supramolecular polymer[2]. Hmt (hexamethyl…     

Synthesis and Characterization of a Trinuclear Zinc(Ⅱ) Complex with Schiff Base (1R,2R)-(-)-Diaminocyclohexane- N,N'-biscarboxyl-salicylidene)

A homochiral complex, Zn3(Hsalen)2(Py)4(H2O)2 (salen = (1R,2R)-(-)-diamino-cyclohexane-N,N'-biscarboxyl-salicylidene) 1, has been synthesized by solvothermal procedure and characterized by IR, microanalysis, TGA, powder and single-crystal X-ray crystallography. It crystallizes in monoclinic space group P2 with a = 10.9439(7), b = 10.1722(6), c = 27.3450(17), β = 97.5060(10)o, V = 3018.1(3) 3, Z = 2, Zn3(Hsalen)2(Py)4(H2O)2, Mr = 1363.33, Dc = 1.500 g/cm3, F(000) = 1408, μ = 1.257 mm-1, GOOF = 1.042, the final R = 0.0601 and wR = 0.1464 for 10322 observed reflections with I 2σ(I). The coordination polymer 1 possesses a 1D infinite zigzag chain architecture constructed by strong hydrogen bonding interactions and the polymeric chains are further assembled into a 2D supramolecular network structure via C-H···π interactions between the cyclohexane and aromatic rings of the ligand of adjacent chains. Simultaneously, π···π stacking interactions play an important role in forming the 2D supramolecular framework.     

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.     

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.     

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.     

Hydrothermal Syntheses and Crystal Structures of Zn(Ⅱ) and Co(Ⅱ) Complexes Constructed from 5-Methoxyisophthalic Acid and 1,10-Phenanthroline Ligands

Two new one-dimensional coordination polymers,[Zn(L)(phen)]n 1 and {[Co2(L)2(phen)2]·2H2O}n 2(H2L=5-methoxyisophthalic acid,phen=1,10-phenanthroline),have been obtained by hydrothermal conditions.According to their single-crystal X-ray diffraction analyses,complex 1 crystallizes in the monoclinic system,space group P2/c with a=8.9195(11),b=12.3620(15),c=17.0211(18),β=106.690(5)o,V=1797.7(4)3,the final R=0.0298 and wR=0.0715 for 3351 independent reflections with Rint=0.0353.Complex 2 crystallizes in the monoclinic system,space group C2/c with a=24.981(4),b=11.1204(19),c=18.125(3),β=132.5620(10)o,V=3708.5(11)3,the final R=0.0349 and wR=0.0914 for 3424 independent reflections with Rint=0.0214.Both 1 and 2 show L-bridged one-dimensional chain.1 and 2 are further assembled by π-π and hydrogen bonding interactions into 2-D layer structures,and they also display 3-D supramolecular frameworks through their other hydrogen bonds.Zn(Ⅱ) ion is five-coordinated with a distorted trigonal bipyramidal coordination geometry,while Co(Ⅱ) ion is six-coordinated and resides in a distorted octahedral coordination geometry.Additionally,complex 1 shows fluorescence in the solid state at room temperature.     

Syntheses,Structures,and Properties of Three New Polymers Based on Flexible and Rigid Ligands

Three new supramolecular polymers, [(IP)(H_2SO_4)(H_2O)](1), [(H_2SDC)(BPA)](2) and [Mn(SDC)(IP)_2]_n (3), have been constructed by three modes(rigid IP, rigid SDC + flexible BPA, rigid IP + rigid SDC). Polymers 1 and 2 are supramolecular structures, assembled by hydrogen bonds and π···π interactions. X-ray structure analysis of 3 shows waved 1D chains which form a 3D supramolecular network by hydrogen bonds and π···π interactions. Solid-state properties of thermal stability, luminescent properties, and X-ray powder diffractions for these crystalline materials have also been investigated, and polymer 3 is considered to be a good stable luminescence material.     

A One-dimensional Metal-organic Framework of Eu(Ⅲ) from Triazine-based Flexible Polycarboxylate and Bidentate Nitrogen Donor Ligand

A new Eu(III) complex from 2,2'-bipyridine(2,2'-bipy) and 1,3,5-triazine-2-4,6-tri(L-alanine)(H3L), {[Eu(L)(2,2'-bipy)](H2O)}n(1), has been synthesized and characterized. The X-ray structure analysis reveals that 1 is an infinite one-dimensional chain-like coordination polymer consisting of dinuclear lanthanide building blocks. The 1D chains are further assembled into a 2D supramolecular architecture through π···π interaction among chains. Crystal data for 1: Eu C22H25N8O7, triclinic, space group P1, a = 11.3965(1), b = 11.5112(6), c = 12.0404(1)?, α = 61.970(11), β = 86.698(15), γ = 65.254(12)°, V = 1247.0(2) ?3 and Z = 2. Solid-state photoluminescence property of 1 was investigated, which exhibited remarkable red luminescence emissions with high quantum yield up to 37%.     

Syntheses and Crystal Structures of Two Copper(Ⅱ) Coordination Polymers Derived from Aromatic Carboxylic Acids and Bis(imidazoles) Ligands

Two compounds have been obtained by the reaction of metal(Cu(II)), 4,4?-bis(imidazol-l-yl)diphenyl thioether(BIDPT) with two carboxylic acids, 4,4?-oxydibenzoic acid(H_2oba) and phthalic acid(H_2pht). The crystal structures of the resulting compounds, namely {[Cu(BIDPT)(oba)]·H2O}n(1) and {Cu(BIDPT)(pht)}n(2), have been determined by single-crystal X-ray diffraction analysis. Compound 1 is of orthorhombic system, space group Pbcn with a = 27.8310(3), b = 10.7791(1), c = 19.3913(2) ?, V = 5817.0(3) ?3 and Mr = 656.15. Compound 2 belongs to the monoclinic system, space group C2/c with a = 18.2678(2), b = 11.0259(1), c = 22.906(2) ?, β = 97.727(2)o, V = 4571.8(8) ?3 and Mr = 545.04. Structural analyses reveal that compounds 1 and 2 respectively exhibit two-dimensional(2D) wavy and corrugated layer structures. Through intermolecular hydrogen bonding, compound 1 is assembled into a 3D supramolecular structure. The thermal stability and ultraviolet spectroscopy properties of the two compounds are also investigated.     

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.