One-dimensional Polymeric Chains Research Articles

Polymeric structure of a coproporphyrin I ruthenium(II) complex: a powder diffraction study.

Porphyrin complexes of ruthenium are widely used as models for the heme protein system, for modelling naturally occurring iron-porphyrin systems and as catalysts in epoxidation reactions. The structural diversity of ruthenium complexes offers an opportunity to use them in the design of multifunctional supramolecular assemblies. Coproporphyrins and metallocoproporphyrins are used as sensors in bioassay and the potential use of derivatives as multiparametric sensors for oxygen and H+ is one of the main factors driving a growing interest in the synthesis of new porphyrin derivatives. In the coproporphyrin I RuII complex catena-poly[[carbonylruthenium(II)]-μ-2,7,12,17-tetrakis[2-(ethoxycarbonyl)ethyl]-3,8,13,18-tetramethylporphyrinato-κ5N,N',N'',N''':O], [Ru(C44H52N4O8)(CO)]n, the RuII centre is coordinated by four N atoms in the basal plane, and by axial C (carbonyl ligand) and O (ethoxycarbonylethyl arm from a neighbouring complex) atoms. The complex adopts a distorted octahedral geometry. Self-assembly of the molecules during crystallization from a methylene chloride-ethanol (1:10 v/v) solution at room temperature gives one-dimensional polymeric chains.

Synthesis, crystal structure, and fluorescent property of a 1D Pb(II) coordination polymer containing unique helical chains based on 4,4′-oxydiphthalate

ABSTRACT A one-dimensional Pb(II) complex [Pb2(H2ODPT)2(H2O)7·H2O]n (1) (H4ODPT = 4,4′-Oxydiphthalic acid) has been synthesized and characterized using single crystal X-ray diffraction, IR, and elemental analysis. Single-crystal X-ray diffraction analysis revealed that complex 1 is a one-dimensional chain polymer containing unique helical chains. Adjacent 1D chains are linked by π–π interaction, intermolecular and intramolecular O–H···O hydrogen bonds to form a three-dimensional supramolecular structure. The thermal stability and photoluminescent property of the title complex have been investigated.

Bulk characterization in a Monte Carlo particle-deposition model with a novel adherence-potential barrier

The aim of this work is to analyze in more depth a model of particle deposition by characterizing different parameters such as profile density, bonds and perimeter, and substrate coverage, all being involved in the description of deposits as bulk. Thus, this study is an extension of a previous work on non-equilibrium interface-growth systems where two different interface-growth models, called Standard Adherence Rule Model and Potential Adherence Rule Model, were characterized. In this work, bulk characterization is implemented for the complete range of Peclet numbers. The zones of density profile (Near-Wall, Plateau, and Active-Growth) are studied by proposing an adjustment for each of them and determining the full-setting density profile depending on the Peclet number. The density profiles are compared with other one- and two-stage models. Furthermore, an algorithm is proposed to calculate the number of bonds of the particles and the perimeter that a substrate forms over time. Finally, to analyze the coating, its temporal behavior is adjusted to an exponential function by comparing the results with those found for Random Sequential Adsorption models which describe systems like colloidal particles on solid substrates, adsorption of proteins at mineral surfaces, or oxidation of one-dimensional polymer chains.

Synthesis, characterization, antibacterial, and antifungal activities of one-dimensional O−H···O hydrogen-bonded Cu(II) and Ni(II) complexes

ABSTRACTTwo Schiff base complexes, [Cu(HL)2], 1 and [Ni(HL)2], 2 [H2L = 2–((E)–(2–hydroxyethylimino)methyl)–1–naptaphenol] have been synthesized and characterized by elemental analysis, 1H NMR, 13C NMR, IR spectroscopy, and X-ray diffraction. In the crystalline architecture of 1 and 2, intermolecular O−H···O hydrogen bonds link the molecules which form one-dimensional polymeric chain structure along the c axis. C−H···O and C−H···π intermolecular interaction also connect the molecules in the structures which form to 3D structures of 1 and 2. The ligand and metal complexes 1 and 2 were screened for antibacterial and antifungal activities.

Novel binuclear and polymeric diorganotin (IV) complexes with N-nicotinyl phosphoramides: Synthesis, characterization, structural studies and anticancer activity

Two new diorganotin complexes with formula {SnCl2(CH3)2L1}2 (C1), L1 = N-nicotinyl, N′,N″-bis(diethylamine) phosphoric triamide and {SnCl2(CH3)2L2}n (C2), L2 = N-nicotinyl, N′,N″-bis(cyclopentylamine) phosphoric triamide were synthesized and characterized by IR and NMR spectroscopy, and elemental analysis. Single crystal X-ray diffraction structural analyses confirmed all-trans and cis–trans configurations for distorted octahedral geometry in C1 and C2, respectively. Also, it revealed that the coordination of L1 and L2 to Sn atom results to a binuclear arrangement in C1 and one-dimensional polymeric chain in C2. The relative stability of M1 (SnCl2(CH3)2L1) and M2 (SnCl2(CH3)2L2) units in binuclear and polymeric arrangements were compared using density functional theory (DFT) calculations. Based on theoretical findings, M1 and M2 prefer polymeric chain structure from energy point of view though the stability difference of M1, in two arrangements, was much lower compared to stability difference of M2. Furthermore, nature of bonds and Sn–ligand interactions was studied by NBO analyses. In vitro cytotoxic assay of complexes against breast cancer cell lines MCF-7, MDA-MB-468 and T47-Dhuman, were also reported. MDA-MB-468 cells are exquisitely sensitive to cell death induced by C1 and C2 complexes treatment. C1 complex exhibited higher anticancer activity, compared to C2, which can be attributed to larger ClSnCl angle in C1.

Supramolecular architectures in Co(II) and Cu(II) complexes with thiophene-2-carboxylate and 2-amino-4,6-dimethoxypyrimidine ligands.

The coordination chemistry of mixed-ligand complexes continues to be an active area of research since these compounds have a wide range of applications. Many coordination polymers and metal-organic framworks are emerging as novel functional materials. Aminopyrimidine and its derivatives are flexible ligands with versatile binding and coordination modes which have been proven to be useful in the construction of organic-inorganic hybrid materials and coordination polymers. Thiophenecarboxylic acid, its derivatives and their complexes exhibit pharmacological properties. Cobalt(II) and copper(II) complexes of thiophenecarboxylate have many biological applications, for example, as antifungal and antitumor agents. Two new cobalt(II) and copper(II) complexes incorporating thiophene-2-carboxylate (2-TPC) and 2-amino-4,6-dimethoxypyrimidine (OMP) ligands have been synthesized and characterized by X-ray diffraction studies, namely (2-amino-4,6-dimethoxypyrimidine-κN)aquachlorido(thiophene-2-carboxylato-κO)cobalt(II) monohydrate, [Co(C5H3O2S)Cl(C6H9N3O2)(H2O)]·H2O, (I), and catena-poly[copper(II)-tetrakis(μ-thiophene-2-carboxylato-κ(2)O:O')-copper(II)-(μ-2-amino-4,6-dimethoxypyrimidine-κ(2)N(1):N(3))], [Cu2(C5H3O2S)4(C6H9N3O2)]n, (II). In (I), the Co(II) ion has a distorted tetrahedral coordination environment involving one O atom from a monodentate 2-TPC ligand, one N atom from an OMP ligand, one chloride ligand and one O atom of a water molecule. An additional water molecule is present in the asymmetric unit. The amino group of the coordinated OMP molecule and the coordinated carboxylate O atom of the 2-TPC ligand form an interligand N-H...O hydrogen bond, generating an S(6) ring motif. The pyrimidine molecules also form a base pair [R2(2)(8) motif] via a pair of N-H...N hydrogen bonds. These interactions, together with O-H...O and O-H...Cl hydrogen bonds and π-π stacking interactions, generate a three-dimensional supramolecular architecture. The one-dimensional coordination polymer (II) contains the classical paddle-wheel [Cu2(CH3COO)4(H2O)2] unit, where each carboxylate group of four 2-TPC ligands bridges two square-pyramidally coordinated Cu(II) ions and the apically coordinated OMP ligands bridge the dinuclear copper units. Each dinuclear copper unit has a crystallographic inversion centre, whereas the bridging OMP ligand has crystallographic twofold symmetry. The one-dimensional polymeric chains self-assemble via N-H...O, π-π and C-H...π interactions, generating a three-dimensional supramolecular architecture.

Synthesis, Crystal Structure and Properties of Two Novel Complexes: [Cu4(2,2′-bipy)4Cl4(Hima)4].4H2O and [Co2(H2Pimdc)6(H2PDA)3].6H2O

Two novel metal-organic complexes [Cu4(2,2′-bipy)4Cl4(Hima)4].4H2O (1), [Co2(H2Pimdc)6(H2PDA)3].6H2O(2)(Hima=1H-imidazole-1-acetic acid, 2,2′-bipy=2,2′-bipyridyl, H2Pimdc=2-propyl-4,5-imidazoledicarboxylic acid, H2PDA=1.4-Phenylenediacetic acid) have been synthesized and characteristic by IR spectrum, elemental analysis, cyclic voltammetry, single-crystal X-ray diffraction. X-ray structure analysis shows that complex 1 is a one-dimensional chain polymer and complex 2 is zero-dimensional, and then complex 1 becomes three-dimensional via hydrogen bonds and π-π stacking interactions, and complex 2 becomes three-dimensional only by complicated hydrogen bonds.

Synthesis, structural characterization and thermal properties of a new copper(II) one-dimensional coordination polymer based on bridgingN,N′-bis(2-hydroxybenzylidene)-2,2-dimethylpropane-1,3-diamine and dicyanamide ligands

The design and synthesis of polymeric coordination compounds of 3d transition metals are of great interest in the search for functional materials. The coordination chemistry of the copper(II) ion is of interest currently due to potential applications in the areas of molecular biology and magnetochemistry. A novel coordination polymer of Cu(II) with bridging N,N'-bis(2-hydroxyphenyl)-2,2-dimethylpropane-1,3-diamine (H2L-DM) and dicyanamide (dca) ligands, catena-poly[[[μ2-2,2-dimethyl-N,N'-bis(2-oxidobenzylidene)propane-1,3-diamine-1:2κ(6)O,N,N',O':O,O']dicopper(II)]-di-μ-dicyanamido-1:2'κ(2)N(1):N(5);2:1'κ(2)N(1):N(5)], [Cu2(C19H20N2O2)(C2N3)2]n, has been synthesized and characterized by CHN elemental analysis, IR spectroscopy, thermal analysis and X-ray single-crystal diffraction analysis. Structural studies show that the Cu(II) centres in the dimeric asymmetric unit adopt distorted square-pyramidal geometries, as confirmed by the Addison parameter (τ) values. The chelating characteristics of the L-DM(2-) ligand results in the formation of a Cu(II) dimer with a double phenolate bridge in the asymmetric unit. In the crystal, the dimeric units are further linked to adjacent dimeric units through μ1,5-dca bridges to produce one-dimensional polymeric chains.

CB-TE2A(+)·Cl(-)·3H2O: a short intermolecular hydrogen bond between zwitterionic bicyclo[6.6.2]tetraamine macrocycles.

1,4,8,11-Tetraazabicyclo[6.6.2]hexadecane-4,11-diacetic acid (CB-TE2A) is of much interest in nuclear medicine for its ability to form copper complexes that are kinetically inert, which is beneficial in vivo to minimize the loss of radioactive copper. The structural chemistry of the hydrated HCl salt of CB-TE2A, namely 11-carboxymethyl-1,8-tetraaza-4,11-diazoniabicyclo[6.6.2]hexadecane-4-acetate chloride trihydrate, C16H31N4O4(+)·Cl(-)·3H2O, is described. The compound crystallized as a positively charged zwitterion with a chloride counter-ion. Two of the amine groups in the macrocyclic ring are protonated. Formally, a single negative charge is shared between two of the carboxylic acid groups, while one chloride ion balances the charge. Two intramolecular hydrogen bonds are observed between adjacent pairs of N atoms of the macrocycle. Two intramolecular hydrogen bonds are also observed between the protonated amine groups and the pendant carboxylate groups. A short intermolecular hydrogen bond is observed between two partially negatively charged O atoms on adjacent macrocycles. The result is a one-dimensional polymeric zigzag chain that propagates parallel to the crystallographic a direction. A second intermolecular interaction is a hydrogen-bonding network in the crystallographic b direction. The carbonyl group of one macrocycle is connected through the three water molecules of hydration to the carbonyl group of another macrocycle.

Organisation and ordering of 1D porphyrin polymers synthesised by on-surface Glaser coupling.

One-dimensional polymer chains consisting of π-conjugated porphyrin units are formed via Glaser coupling on a Ag(111) surface. Scanning probe microscopy reveals the covalent structure of the products and their ordering. The conformational flexibility within the chains is investigated via a comparision of room temperature and cryogenic measurements.

Synthesis of ordered conjugated polycyclic aromatic hydrocarbon polymers through polymerization reaction on Au(111)

One-dimensional π-conjugated polymer chains with variable lengths have been synthesized successfully via thermal polymerization reaction on the Au(111) surface. Such polymer chains form parallel arrays along specific directions according to the initial assembly orientations of the close-packed Br-BTTN precursors.

Target-triggered autonomous assembly of DNA polymer chains and its application in colorimetric nucleic acid detection

A novel target-triggered DNA autonomous assembly pathway for the formation of one-dimensional DNA polymer chains was proposed based on the catalyzed hairpin assembly and sticky end self-assembly, which led to an enzyme-free and signal amplified gold nanoparticle (AuNP) based colorimetric nucleic acid assay with picomolar sensitivity and specificity.

Crystal structure of a one-dimensional coordination polymer of tin(IV) bromide with 1,4-di-thiane.

The title compound, [SnBr4(C4H8S2)] {systematic name: catena-poly[[tetrabromidotin(IV)]-μ-1,4-dithiane-κ2 S:S′]}, represents the first 1,4-di­thiane complex with tin as coordination centre. The asymmetric unit consist of half a formula unit with the tin(IV) atom at the centre of symmetry at 0,0,1/2 (Wyckoff symbol b) and a centrosymmetric 1,4-di­thiane mol­ecule with the centre of symmetry in 1/2,0,1 (Wyckoff symbol c). The tin(IV) atom is coordinated in a distorted octa­hedral manner by the four bromine atoms and two sulfur atoms of two 1,4-di­thiane mol­ecules in a trans-position. Sn—Br [mean value: 2.561 (5) Å] and Sn—S distances [2.6546 (6) Å] are in the typical range for octa­hedrally coordinated tin(IV) atoms and the di­thiane mol­ecule adopts a chair conformation. The one-dimensional polymeric chains propagate along the [101] direction with weak inter­molecular Br⋯Br [3.5724 (4) Å] between parallel chains and weak Br⋯H inter­actions [2.944–2.993 Å] within the chains.

A Micromechanically Based Constitutive Model for the Inelastic and Swelling Behaviors in Double Network Hydrogels

This paper presents a micromechanically based constitutive model within the framework of the continuum mechanics to characterize the inelastic elastomeric and swelling behaviors of double network (DN) hydrogels, such as the stress-softening, necking instability, hardening, and stretch-induced anisotropy. The strain-energy density function of the material is decomposed into two independent contributions from the tight and brittle first network and the soft and loose second network, each of which is obtained by integrating the strain energy of one-dimensional (1D) polymer chains in each direction of a unit sphere. The damage process is derived from the irreversible breakages of sacrificial chains in the first network and characterized by the directional stretch-dependent evolution laws for the equivalent modulus and the locking stretch in the non-Gauss statistical model of a single polymer chain. The constitutive model with the optimized-material evolution law predicts stress–stretch curves in a good agreement with the experimental results during loading, unloading, and reloading paths for both ionic and covalent DN hydrogels. The deformation-induced anisotropy is investigated and demonstrated by the constitutive model for the free swelling of damaged specimen. The constitutive model is embedded into the finite-element (FE) procedure and proved to be efficient to model the necking and neck propagation in the plane-strain uniaxial elongation. Based on the procedure, the effects of imperfection and boundary conditions on the loading path and the material evolution during different stages of deformation are investigated.

A New 3-D Mn(II) Naphthoic Acid Complex [Mn(1,4-DNC)(DMA)]n (1,4-DNC = 1,4-Naphthalenedicarboxylate, DMA = Dimethylacetamide)

A new 3-D Mn(II)-organic extended framework with a 1,4-naphthalenedicarboxylate ligand, [Mn(1,4-DNC)(DMA)]n (1), was obtained by the solvothermal reaction of MnCl2⋅4H2O and 1,4-naphthalenedicarboxylate (1,4-H2DNC) in dimethylacetamide organic solvents. Each Mn(II) atom is five-coordinated in a triagonal–bipyramidal coordination environment by four carboxylate O atoms from four different 1,4-DNC2– ligands and one O atom from a terminal DMA molecule. The neighboring Mn(II) atoms are doubly bridged by 1,4-DNC2– ligands to give a one-dimensional coordination polymeric chain [Mn(COO)2]n, and each chain is connected to four other different chains through µ4-kO1: kO2: kO3: kO4 1,4-DNC2– ligands to form a 3-D network of 1.

Silver(I) complexes as efficient source for silver oxide nanoparticles with catalytic activity in A3 coupling reactions

New silver(I) complexes [Ag7(μ4-Cl)(μ3-Cl)2(μ2-Cl)3(MPI)6] (1), and [Ag(μ3-I)(BI)]n (2) [MPI=1-(4-methoxyphenyl)-1H-imidazole; BI=1-Benzylimidazole] have been prepared starting with AgX (X=Cl, I) and 1-(4-methoxyphenyl)-1H-imidazole/1-Benzylimidazole. The complexes have been characterized by elemental analysis, IR, 1H NMR, and electronic absorption spectroscopy. Molecular structure of the complexes 1 and 2 were determined crystallographically. Complex 1 has a twofold axis with Ag3 in special position and bisecting the Ag4–Ag4′ vector. It contains six 1-(4-methoxyphenyl)-1H-imidazole molecules and seven chlorine atoms bridging the seven silver atoms. Complex 2 exists as a one-dimensional (1D) polymeric chain of [(μ3-I)Ag(μ3-I)Ag] fragments bridged via the 1-Benzylimidazole ligand. The weak argentophilic Ag⋯Ag interaction distances in complexes 1 and 2 are 3.1014(4)Å–3.2998(15)Å, respectively. The complexes 1 and 2, yielded silver oxide nanoparticles on pyrolysis and were characterized by PXRD and TEM. The catalytic properties of the resulting silver oxide nanoparticles and the silver(I) complexes have also been studied for A3-coupling of amines, alkynes and aldehydes in microwave which gave moderate to good yields of propargylamines. Silver(I) complexes exhibit higher catalytic activity compared to silver oxide nanoparticles. The silver oxide nanoparticles as well as silver(I) complexes could be separated easily from the reaction mixture and reused at least four to five times without significant loss of the catalytic activity.

One-dimensional Cu(II) coordination polymers containing C2h-symmetric 1,1':4',1''-terphenyl-3,3'-dicarboxylate linkers.

Two new one-dimensional Cu(II) coordination polymers (CPs) containing the C2h-symmetric terphenyl-based dicarboxylate linker 1,1':4',1''-terphenyl-3,3'-dicarboxylate (3,3'-TPDC), namely catena-poly[[bis(dimethylamine-κN)copper(II)]-μ-1,1':4',1''-terphenyl-3,3'-dicarboxylato-κ(4)O,O':O'':O'''] monohydrate], {[Cu(C20H12O4)(C2H7N)2]·H2O}n, (I), and catena-poly[[aquabis(dimethylamine-κN)copper(II)]-μ-1,1':4',1''-terphenyl-3,3'-dicarboxylato-κ(2)O(3):O(3')] monohydrate], {[Cu(C20H12O4)(C2H7N)2(H2O)]·H2O}n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X-ray crystallography. The 3,3'-TPDC bridging ligands coordinate the Cu(II) ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one-dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one-dimensional coordination polymer chains, forming a two-dimensional network in (I) and a three-dimensional network in (II).

Two different anionic manganese(II) coordination polymers constructed through dicyanamide coordination bridges

In order to explore new metal coordination polymers and to search for new types of ferroelectrics among hybrid coordination polymers, two manganese dicyanamide complexes, poly[tetramethylammonium [di-μ3-dicyanamido-κ(6)N(1):N(3):N(5)-tri-μ2-dicyanamido-κ(6)N(1):N(5)-dimanganese(II)]], {[(CH3)4N][Mn2(NCNCN)5]}n, (I), and catena-poly[bis(butyltriphenylphosphonium) [[(dicyanamido-κN(1))manganese(II)]-di-μ2-dicyanamido-κ(4)N(1):N(5)]], {[(C4H9)(C6H5)3P]2[Mn(NCNCN)4]}n, (II), were synthesized in aqueous solution. In (I), one Mn(II) cation is octahedrally coordinated by six nitrile N atoms from six anionic dicyanamide (dca) ligands, while the second Mn(II) cation is coordinated by four nitrile N atoms and two amide N atoms from six anionic dca ligands. Neighbouring Mn(II) cations are linked together by μ-1,5- and μ-1,3,5-bridging dca anions to form a three-dimensional polymeric structure. The anionic framework exhibits a solvent-accessible void of 289.8 Å(3), amounting to 28.0% of the total unit-cell volume. Each of the cavities in the network is occupied by only one tetramethylammonium cation. In (II), each Mn(II) cation is octahedrally coordinated by six nitrile N atoms from six dca ligands. Neighbouring Mn(II) cations are linked together by double dca bridges to form a one-dimensional polymeric chain, and C-H...N hydrogen-bonding interactions are involved in the formation of the one-dimensional layer structure.

Crystal structure and fluorescent properties of a 1D Zn(II) coordination polymer based on 5-nitro-1,3-benzenedicarboxylic acid

A one-dimensional Zn(II) complex [Zn(Im)2(NO2–BDC)]n (1) (Im = Imdazole, NO2–H2BDC = 5-nitro-1,3- benzenedicarboxylic acid) is synthesized and characterized using single crystal X-ray diffraction, IR spectroscopy and elemental analysis. Single crystal X-ray diffraction analysis reveals that complex 1 is a one-dimensional chain polymer with a Zn⋯Zn separation of 9.6190(2) A arranged parallel to the (1 0 0) crystal direction. In addition, the luminescence measurements reveal that complex 1 exhibits strong fluorescent emissions in the solid state at room temperature.

A Series of Cyanoacetato Copper(II) Coordination Polymers with Various N,N′-Ditopic Spacers: Structural Diversity, Supramolecular Robustness, and Magnetic Properties

Five novel copper(II) coordination polymers containing cyanoacetate (cna) anion with various N,N′-ditopic spacers [Cu(cna)2(pyz)]n (1), [Cu(cna)2(bpy)(H2O)2]n (2), [Cu(cna)2(dpe)]n (3), [Cu(cna)2(dpe)]n(H2O)n (4), and [Cu(cna)2(bpa)]n (5) (when pyz = pyrazine, bpy = 4,4′-bipyridyl, dpe = 1,2-di(4-pyridyl)ethylene, and bpa = 1,2-di(4-pyridyl)ethane) were structurally and spectroscopically characterized. Compound 1 shows a two-dimensional (2D) sheet structure constructed from μ2-1,3(syn,anti) coordinative mode of cyanoacetate and μ2-pyz linking adjacent Cu(II) centers. Compound 2 exhibits a one-dimensional (1D) polymeric chain which is formed by μ2-bpy bridging between [Cu(cna)2(H2O)2] units, whereas compounds 3–5 reveal 1D ladder-like structures which are built from double-μ2-dpe/bpa spacers connecting neighboring Cu(II) cyanoacetate dimers. Weak interactions such as hydrogen bonding and N···π and/or C–H···π interactions join the adjacent layers of 1 or polymeric chains of 2–5 to stabilize overall supramol...