Two New Three-dimensional Supramolecular Complexes with 5-Carboxyl-1-carboxymethyl-2-oxidopyridinium: Syntheses and Crystal Structures

Two new supramolecular complexes [MnL(H2O) 4](1) and [ZnL(H2O) 5]·0.25H2O(2) (H2L = 5-carboxy-1-carboxymethyl-2-oxidopyridinium) have been synthesized and structurally characterized by elemental analysis,IR and X-ray single-crystal structure determination. Complex 1 crystallizes in the monoclinic system,space group P21/n with a = 5.1537(2) ,b = 21.2008(9) ,c = 10.9727(4) ,β = 99.182(2) °,V = 1183.54(8) 3,C8H13MnNO9,Mr = 322.13,Dc = 1.808,Z = 4,F(000) = 660,μ = 1.160,R = 0.0372 and wR = 0.0750 for 2217 observed reflections(I > 2σ(I)) . Complex 2 crystallizes in the triclinic system,space group P1 with a = 7.730(2) ,b = 8.030(2) ,c = 11.400(2) ,α = 104.27(3) ,β = 92.93(3) ,γ = 102.67(3) °,V = 664.9(2) 3,C8H15.5ZnNO10.25,Mr = 355.08,Dc = 1.774,Z = 2,F(000) = 365,μ = 1.899,R = 0.0243 and wR = 0.0695 for 2759 observed reflections(I > 2σ(I)) . Their thermal properties have been studied.     

Syntheses,structures, and photoluminescence of three cadmium(II) coordination polymers with flexible bis(benzimidazole) ligands

Three cadmium(II) coordination polymers, [CdBr₂(L₁)] _n (1), [CdI₂(L₂)] _n (2), and Cd₂Br₄(L₃)₂ (3), where L₁?=?1,3-bis(5,6-dimethylbenzimidazole)propane, L₂?=?1,4-bis(5,6-dimethylbenzimidazole)butane, and L₃?=?1,6-bis(5,6-dimethylbenzimidazole)hexane, have been synthesized by hydrothermal methods and characterized by elemental analyses, IR spectra, TGA, PXRD, and X-ray crystallographic diffraction. Complex 1 contains a 1-D helical chain in which CdBr₂ units are linked by L₁. For 2, each CdI₂ is connected by two different conformations of L₂ to form a 1-D zigzag chain. For 3, each CdBr₂ is linked by L₃ bridges to afford a binuclear structure. These results indicate that the spacer length of the ligands play important roles in assembly of Cd(II) coordination polymers. Thermogravimetric analyses and solid-state luminescent properties of the complexes have also been investigated.     

Syntheses,supramolecular structures and properties of six coordination complexes based on 5-sulfosalicylic acid and bipyridyl-like chelates

Six new complexes constructed by 5-sulfosalicylic acid and bipyridyl-like ligands (2,2′-bipy and 1,10-phen), namely [Cu₄(OH)₂(ssal)₂(phen)₄ · 7H₂O] (1), [Cu₄(OH)₂(ssal)₂(bipy)₄ · 2H₂O] (2), [Cd(Hssal)(bipy)] (3), [Cd(HL)₂(phen)₂] (4), [Cr(ssal)(bipy)(H₂O)₂ · 2H₂O] (5) and [Cr(ssal)(phen)₂] (6) (H₃ssal = 5-sulfosalicylic acid, H₂L = p-hydroxybenzenesulfonic acid, bipy = 2,2′-bipy, phen = 1,10-phen) were prepared under hydrothermal conditions and their structures were determined by single-crystal X-ray diffraction. Complexes 1 and 2 are both tetranuclear copper complexes with a stepped topology. In complex 3, a new coordination mode of the Hssal²⁻ group is reported in this work. During the synthetic process of complex 4, in situ decarboxylation of 5-sulfosalicylic acid into p-hydroxybenzenesulfonic acid is involved. Two chromium 5-sulfosalicylates (5 and 6) are reported for the first time. These new complexes display different supramolecular structures by O–H?O, C–H?O hydrogen bonds as well as π?π, C–H?π and O?π interactions. The results of magnetic determination show that ferromagnetic interactions exist in complex 1, however, antiferromagnetic interactions exist in 2.     

Three isomeric copper(II) coordination polymers based on a bis-triazole-bis-amide ligand: Assembly,structures, and luminescent properties

Three copper(II) isomers, [Cu(dtcd)(DNBA)₂]_n (1–3) (HDNBA = 3,5-dinitrobenzoic acid, dtcd = N,N-di(4H-1,2,4-triazole)cyclohexane-1,4-dicarboxamide), were synthesized in a one-pot reaction, and structurally characterized. Polymer 1 shows a 1-D single chain in which dtcd connect adjacent Cu²⁺ ions, while DNBA^? is monodentate. In 2, every two Cu²⁺ ions are linked by carboxylate of a DNBA^? in a chelate-bridging mode into a binuclear unit, which is further connected by dtcd ligands into a 1-D double chain. In 3, dtcd connect Cu²⁺ ions via triazole nitrogens to generate 1-D single chains, which are further extended into a 2-D network by the amide oxygens of a dtcb from an adjacent chain. The pH plays an important role in product distribution of 1–3. The coordination behaviors of dtcd and DNBA^? also influence the final structures. Luminescent properties of 1–3 have been investigated.     

Syntheses,crystal structures,and photophysical properties of two 2-D coordination polymers with different geometries of lead(II)

Two complexes constructed from aromatic acid and N-heterocyclic ligands have been synthesized by hydrothermal reaction: [Pb(cipt)(NDC)]_n (1) [cipt?=?2-(3-chlorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, NDC?=?naphthalene-1,4-dicarboxylic acid] and [Pb(ipm)(BDC)₂]_n (2) [BDC?=?terephthalic acid, ipm?=?5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-2-methoxyphenol]. Single-crystal X-ray analysis shows that 1 exhibits an interesting arm-shaped chain structure. 1-D ladder chain structure is formed by N–H···O bonding interactions and further into a 2-D network by N–H···O hydrogen bonds and interchain π–π stacking interactions. Complex 2 shows a 2-D butterfly wings structure, which has been rarely reported. The structure in 2 has intermolecular N–H···O interactions, which help in construction of the 3-D framework. In 1, the coordination sphere of Pb(II) is hemi-directed, whereas the Pb(II) geometry in 2 is holo-directed. The solid-state fluorescence spectra of 1 and 2 are also investigated, as well as the ligands cipt and ipm.     

Self-assembly of 1-D and 3-D transition-metal coordination polymers based on 4-(1H-l,3-benzimidazol-2-yl)pyridine 1-oxide

Three metal-organic coordination polymers based on 4-(1H-l,3-benzimidazol-2-yl)pyridine 1-oxide (BImPyO) with the molecular structures [Cu₂(C₁₂H₈N₃O)₂]_n (1), [Cu(C₁₂H₈N₃O)]_n (2), and [Zn(C₁₂H₈N₃O)Cl]_n (3) were synthesized under hydrothermal conditions. They showed diverse coordination modes and were further characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray structure analysis, respectively. In 1 and 2, BImPyO generated a 1-D chain by adopting μ₂-kN?:?kN′ coordination to bridge two Cu(II) ions with bis-N-chelation. In 3, by adopting μ₃-kN?:?kN′:kO coordination, BImPyO bridged three crystallographically independent Zn(II) ions to form a 3-D framework; 3 exhibits strong fluorescent emission in the solid state at room temperature.     

Synthesis, crystal structure and magnetic characterization of metal(II) coordination polymers based on 2-carboxyethylphosphonic acid and 1,10-phenanthroline (metal=Cu, Co, Cd)

Three non-isostructural metal(II) coordination polymers (metal=copper, cobalt, cadmium) were synthesized under the same mild hydrothermal conditions (T=408 K) by mixture of the corresponding metal acetate with 2-carboxyethylphosphonic acid and 1,10-phenanthroline (1:1:1 M ratio) and their structures were determined by single-crystal X-ray diffraction. Cu₂(HO₃PCH₂CH₂COO)₂(C₁₂H₈N₂)₂(H₂O)₂ and Cd₂(HO₃PCH₂CH₂COO)₂(C₁₂H₈N₂)₂ are triclinic (space group P-1) with a=7.908(5) Å, b=10.373(5) Å, c=11.515(5) Å, α=111.683(5)°, β=95.801(5)°, γ=110.212(5)° (T=120 K), and a=8.162(5) Å, b=9.500(5) Å, c=11.148(5) Å, α=102.623(5)°, β=98.607(5)°, γ=113.004(5)° (T=293 K), respectively. In contrast, [Co₂(HO₃PCH₂CH₂COO)₂(C₁₂H₈N₂)₂(μ-OH₂)](H₂O) is orthorhombic (space group Pbcn) with a=21.1057(2) Å, b=9.8231(1) Å, c=15.4251(1) Å (T=120 K). For these three compounds, structural features, including H-bond network and the π-π stacking interactions, and thermal stability are reported and discussed. None of the materials present a long-range magnetic order in the range of temperatures investigated from 300 K down to 1.8 K.     

Syntheses and structural characterizations of three transition metal coordination complexes based on flexible 2,4-dichlorophenoxyacetate (2,4-DCP)

Three transition metal coordination complexes, {[Co(2,4-DCP)₂(μ ₂-H₂O)(H₂O)₂]?·?(H₂O)₂} _n (1), [Zn(2,4-DCP)(IN)] _n (2), and [Mn₂(2,4-DCP)₃(DMPY)₂(μ ₂-H₂O)(H₂O)]?·?(2,4-DCP)?·?0.2(H₂O) (3) (2,4-DCP?=?2,4-dichlorophenoxyacetate, IN?=?isonicotinate, DMPY?=?5,5′-dimethyl-2,2′-bipyridine), have been prepared under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. Complex 1 displays a 1-D chain through cobalt and bridging water molecules with Co?···?Co distance of 4.028(2)?Å. Complex 2 shows a 2-D (4,4) net, which is extended into a 3-D supramolecular framework by weak hydrogen-bonding interactions. Complex 3 consists of discrete dinuclear cations, 2,4-DCP counter ions and free water molecules, which are assembled into a packing structure through π?···?π stacking of inversion-related DMPY ligands and hydrogen bonds. Magnetic susceptibility measurements show weak antiferromagnetic interactions in 1. The photoluminescence and lifetime of 2 in the solid state have also been studied.     

Syntheses, crystal structures and fluorescent properties of Cd(II), Hg(II) and Ag(I) coordination polymers constructed from 1H-1,2,4-triazole-1-acetic acid

Three new d¹⁰ coordination polymers, namely [Cd(taa)Cl]_n1, [Hg(taa)Cl]_n2, and [Ag_1.5(taa)(NO₃)_0.5]_n3 (taa=1H-1,2,4-triazole-1-acatate anion) have been prepared and characterized by elemental analysis, IR, and single crystal X-ray diffraction. Compound 1 consists of two-dimensional layers constructed by carboxyl-linked helical chains, which are further linked through carboxyl group to generate a unique 3D open framework. Topological analysis reveals that the structure of 1 can be classified as an unprecedented (3,8)-connected network with the Schläfli symbol (4.5²)₂(4².5⁸.6¹⁴.7³.8). Compound 2 manifests a doubly interpenetrated decorated α-polonium cubic network with the Schläfli symbol of (4¹⁰.6².8³). Compound 3 consists of 2D puckered layers made up of Ag centers and taa⁻ bridges. In addition, all of these compounds are photoluminescent in the solid state with spectra that closely resemble those of the ligand precursor.     

Syntheses,structures, and luminescence of two Zn(II) coordination polymers based on 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole and carboxylates

Reactions of Zn(II) salts, 5-(4-(1H-imidazol-1-yl)phenyl)-1H-tetrazolate (HIPT) and 2-mercaptobenzoic acid or 2-propyl-1H-imidazole-4,5-dicarboxylic acid (H₃PrIDC), result in two mixed-ligand coordination polymers (CPs), [Zn₂(IPT)(DSDB)(OH)]_n (H₂DSDB = 2,2′-disulfanediyldibenzoic acid, 1) and [Zn₂(IPT)(PrIDC)(H₂O)]_n (H₃PrIDC = 2-propyl-1H-imidazole-4,5-dicarboxylic acid, 2). Compound 1 possesses a 2-D structure built by 1-D [Zn(IPT)]_n chains and DSDB^2? connectors, in which the DSDB^2? is generated via in situ reaction from 2-mercaptobenzoic acid. It displays a new intricate 4-nodal {3·4·6·7·8·9}{3·6·7·8·9·10}{3·8·9}{4·6·8} topology. Compound 2 displays a 3-D framework with new 3-connected topology with Schläfli symbol of (4·8·10) (8·12²), in which the 1-D Zn-carboxylate chains were bridged by 3-connected IPT^? ligands. The thermal stabilities and luminescence properties of 1 and 2 have also been studied. The compounds exhibit intense solid-state fluorescent emissions at room temperature.     

Hydrothermal synthesis,structure, and photoluminescence of four complexes based on 1H-imidazole-4,5-dicarboxylate or 1H-imidazole-2-carboxylate ligands

Four complexes, [Ag₄(bipy)₂(Himdc)₂(H₂O)₂] _n (1), [Ag(H₂imdc)] _n (2), [K(H₃imdc)(H₂imdc)(H₂O)₂] _n (3), and [Cu(Himc)₂] (4) (H₃imdc?=?1H-imidazole-4,5-dicarboxylic acid, H₂imc?=?1H-imidazole-2-carboxylic acid, and bipy?=?4,4′-bipyridine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis and elemental analysis. The obtained complexes exhibit different coordination structures; 1 contains a 2-D supramolecular layer based on two chains arraying uniformly in an ABAB manner. Compound 2 displays sawtooth-shaped 1-D chains extending to 2-D layers via hydrogen bond interactions. Compound 3 possesses a 3-D framework structure based on a 1-D chain via hydrogen bonding interactions. Compound 4 has a 3-D framework structure bearing a pcu-type topology. In addition, the photoluminescence for 1 has been investigated.     

Syntheses,crystal structures,and catalytic activities of three new Cu(II) coordination polymers based on 2-(1H-1,2,4-triazole)-1-acetic acid

Three new coordination polymers, {[Cu(trza)(2,2′-bipy)(H₂O)]?·?(ClO₄)} _n (1), {[Cu(trza)(2,2′-bipy)(H₂O)]?·?(BF₄)} _n (2), and {[Cu(trza)(4,4′-bipy)]?·?(H₂O)?·?(ClO₄)} _n (3) (Htrza?=?2-(1H-1,2,4-triazole)-1-acetic acid), have been synthesized and characterized by single-crystal X-ray diffraction analysis. Both 1 and 2 exhibit 1-D chain structure while 3 displays 2-D layer structure. The catalytic activities of 1 and 3 in the green oxidative coupling of 2,6-dimethylphenol have been investigated.     

Syntheses,structures, and fluorescent properties of four Co(II) coordination polymers based on 5-hydroxyisophthalic acid and structurally related bis(benzimidazole) ligands

Four cobalt(II) coordination polymers, {[Co(HO-BDC)(bbp)]}_n (1), {[Co(HO-BDC)(bmbp)₂]·(H₂O)₂}_n (2), {[Co(HO-BDC)(bbb)]}_n (3), and {[Co₂(HO-BDC)₂(bmbb)₂]·(H₂O)₃}_n (4), where HO-H₂BDC?=?5-hydroxyisophthalic acid, bbp = 1,3-bis(benzimidazol-1-yl)propane, bmbp = 1,3-bis(2-methyl-benzimidazol-1-yl)propane, bbb = 1,4-bis(benzimidazol-1-yl)butane, and bmbb = 1,4-bis(2-methyl-benzimidazol-1-yl)butane, have been synthesized and characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, thermogravimetric analyses, and fluorescence properties. Compounds 1 and 3 are 4-connected 2-D networks with (4⁴·6²) topology. Compound 2 is a 1-D chain, while 4 features a 1-D ladder. These 1-D and 2-D complexes are further connected by hydrogen bonds to form 3-D supramolecular architectures. Complexes 1–4 showed very strong yellow luminescence emission.     

1-D Chain lanthanide coordination polymers based on mixed 2,4-dichlorophenoxyacetate and 1,10-phenanthroline ligands: crystal structures and luminescent properties

Two new isostructural 1-D lanthanide coordination polymers, {[Ln(2,4-dcp)₃(phen)] _n [(Ln?=?Eu (1); Tb (2)], [2,4-dcp?=?2,4-dichlorophenoxyacetate, phen?=?1,10-phenanthroline], were obtained under hydrothermal conditions and characterized by IR spectroscopy, elemental analyses, thermogravimetry analyses, powder X-ray diffraction, and single-crystal X-ray diffraction. Both structures exhibit similar 1-D infinite chains with a {Ln₂(2,4-dcp)₆(phen)₂} dimeric repeat unit, with lanthanides in an eight-coordinate environment. The results of thermal analysis indicate that 1 and 2 are quite stable to heat. 3-D fluorescence spectra of 1 and 2 were detected at room temperature under excitation and the emission wavelengths of 250–460?nm and 420–750?nm with the same interval of 5?nm, respectively. Interestingly, 1 and 2 possess longer fluorescence lifetimes than other complexes (τ?=?1.61?ms for 1 at 611?nm; 1.79?ms for 2 at 543?nm).     

Ligand-controlled assembly of Cd(II) coordination polymers based on mixed ligands of naphthalene-dicarboxylate and dipyrido[3,2-d:2′,3′-f]quinoxaline: From 0D+1D cocrystal, 2D rectangular network (4,4), to 3D PtS-type architecture

Three novel Cd(II) coordination polymers, namely, [Cd(Dpq)(1,8-NDC)(H₂O)₂][Cd(Dpq)(1,8-NDC)]·2H₂O (1), [Cd(Dpq)(1,4-NDC)(H₂O)] (2), and [Cd(Dpq)(2,6-NDC)] (3) have been obtained from hydrothermal reactions of cadmium(II) nitrate with the mixed ligands dipyrido [3,2-d:2′,3′-f]quinoxaline (Dpq) and three structurally related naphthalene-dicarboxylate ligands [1,8-naphthalene-dicarboxylic acid (1,8-H₂NDC), 1,4-naphthalene-dicarboxylic acid (1,4-H₂NDC), and 2,6-naphthalene-dicarboxylic acid (2,6-H₂NDC)]. Single-crystal X-ray diffraction analysis reveals that the three polymers exhibit novel structures due to different naphthalene-dicarboxylic acid. Compound 1 is a novel cocrystal of left- and right-handed helical chains and binuclear complexes and ultimately packed into a 3D supramolecular structure through hydrogen bonds and π-π stacking interactions. Compound 2 shows a 2D rectangular network (4,4) bridged by 1,4-NDC with two kinds of coordination modes and ultimately packed into a 3D supramolecular structure through inter-layer π-π stacking interactions. Compound 3 is a new 3D coordination polymer with distorted PtS-type network. In addition, the title compounds exhibit blue/green emission in solid state at room temperature.     

Syntheses and crystal structures of Zn(II) and Co(II) complexes with ofloxacin and enoxacin

[Zn(Ofl) · (H₂O)] · 2H₂O (1) and [Co(Enox)₂] · 4H₂O (2) were obtained by hydrothermal reactions. The solid-state structures have been characterized by IR spectroscopy and single crystal X-ray diffraction analyses. Complex 1 crystallizes in the triclinic system, space group P 1, with lattice parameters a = 9.2923(5), b = 11.3432(6), c = 17.7722(10) Å, α = 92.839(3), β = 94.826(3), γ = 91.909(3)°, V = 1863.01(18) ų, Z = 2, D _Calcd = 1.494 mg m^?3. The coordination environment around Zn²⁺ is a slightly distorted square pyramid. Complex 2 crystallizes in the triclinic system, space group P2(1)/c, with lattice parameters a = 5.97980(10), b = 21.4183(3), c = 13.1539(2) Å, V = 100.2810(10), Z = 2, D _Calcd = 1.526 mg m^?3, Co(II) ion is a distorted octahedral geometry.     

Auxiliary aromatic-acid effect on the structures of a series of Zn coordination polymers: Syntheses, crystal structures, and photoluminescence properties

Five novel Zn^II-(pyridyl)imidazole derivative coordination polymers, [Zn(L)₂] (1), [Zn₂(μ₃-OH)L(m-BDC)] (2), [Zn₂(μ₃-OH)L(p-BDC)]·H₂O (3), [Zn₂L(BTC)(H₂O)]·2.5H₂O (4) and [Zn_3.5(μ₃-OH)L₂(BTEC)(H₂O)]·H₂O (5) (L=4-((2-(pyridine-2-yl)-1H-imidazol-1-yl)methyl)benzoic acid, p-H₂BDC=1,4-benzenedicarboxylic acid, m-H₂BDC=1,3-benzenedicarboxylic acid, H₃BTC=1,3,5-benzenetricarboxylic acid, H₄BTEC=1,2,4,5-benzenetetracarboxylic acid), were successfully synthesized under hydrothermal conditions through varying auxiliary aromatic-acid ligands and structurally characterized by X-ray crystallography. Compound 1 exhibits a 1D chain linked via double L bridges. Compound 2 features a well-known pcu topology with bent dicarboxylate ligand (m-H₂BDC) as an auxiliary ligand, while 3 displays a bcu network with linear dicarboxylate ligand (p-H₂BDC) as an auxiliary ligand. The structure of compound 4 is a novel 3D (3,5)-connected network with (4·6²)(4·6⁴·8²·10·12²) topology. It is interesting that compound 5 shows an intricate (3,4,8)-connected framework with (4·6²)(4²·6³·8)(4²·6⁴)(4²·6¹⁸·7·8⁶·10) topology. In addition, their infrared spectra (IR), X-ray powder diffraction (XPRD) and photoluminescent properties were also investigated in detail.     

Synthesis, crystal structure and properties of two 1D nano-chain coordination polymers constructed by lanthanide with pyridine-3,4-dicarboxylic acid and 1,10-phenanthroline

The hydrothermal reactions of LnCl₃·6H₂O (Ln=Eu, Tb), pyridine-3,4-dicarboxylic acid (3,4-pydaH₂), 1,10-phenthroline (phen) and NaOH in aqueous medium yield two metal-organic hybrid materials, [Eu₂(3,4-pyda)₃(phen)(H₂O)·H₂O]_n (1) and [Tb₂(3,4-pyda)₃(phen)(H₂O)·H₂O]_n (2), respectively. Both compounds have similar topology structure containing one-dimensional nano-chain, which is further assembled into a three-dimensional supramolecular network via π-π stacking interactions and hydrogen bonds. To the best of our knowledge, they represent the first example of nano-chain coordination polymers constructed by 3,4-pydaH₂ and chelate heterocylic ligand. Interestingly, the 3,4-pyda anion exhibits three kinds of coordination modes in these complexes. The coordination modes of 3,4-pyda in complexes 1 and 2 have not been observed in other coordination polymers containing 3,4-pyda ligands. Compounds 1 and 2 exhibit strong fluorescent emission bands in the solid state at room temperature. Their magnetic analyses show that they exhibit different magnetic interactions.