Synthesis,structure, and properties of a new 3D hydrogen-bonded porous coordination polymer

A new coordination polymer, [Cd(HMal)(Bipy)(H₂O) · 2H₂O (I) (H₃Mal is malic acid, Bipy is 4,4′-bipyridine), has been synthesized from H₃Mal and Bipy under hydrothermal conditions and characterized by elemental analysis, IR, TG, and single-crystal X-ray diffraction. The X-ray diffraction analysis reveals that I (C₁₄H₁₆N₂O₇Cd) crystallizes in the orthorhombic system, space group Ibam. The adjacent cadmium(II) atoms were first interconnected by the HMal ligands via carboxylate oxygen atoms and its adjacent hydroxyl group to generate an infinite zigzag [Cd(HMal)] _n chain, which are further linked by Bipy ligands to form a 2D wavelike layer. Interestingly, the adjacent layers are further connected via hydrogen bonds, giving rise to a 3D porous framework with a cross-sectional area of 11.690 × 9.326 Ų. The unit cell parameters for I: a = 8,457(1), b = 22.030(7), c = 23.066(7) V = 4297(2) ų, Z = 4.     

Synthesis,crystal structure,and properties of a new lanthanide tartrate coordination polymer

A new coordination polymer of terbium tartrate [Tb(H₂O)₃(C₄H₅O₆)(C₄H₄O₆)] has been synthesized and crystallizes in the polar space group P4₁ with cell constants a = 6.0415(9), b = 6.0415(9), c = 36.516(7) Å, V = 1332.8(4) ų, Z = 4. The terbium(III) ion of title complex is nine-coordinate through oxygen donors. Four different coordination modes of tartrate occur. This Tb(III) complex exhibits a characteristic luminescence in the visible region upon excitation at 353 nm. The temperature-dependent magnetic properties of the Tb(III) complex were investigated in the temperature range of 2–300 K. Title compound exhibits significant ferroelectric properties at room temperature (remnant polarization 2P _r = 0.160 μC cm^?2, coercive field 2E _c = 44.5 kV cm^?1, saturation of the spontaneous polarization P _s = 0.176 μC cm^?2).     

Synthesis,crystal structure and magnetic properties of 2D bi-layered coordination polymer

A new coordination polymer, [Ni(pydc)(H₂O)₂]?·?H₂O (1) (H₂pydc?=?pyridine-3,4-dicarboxylic acid), have been synthesized by treating Ni(II) nitrate with 3,4-pyridinedicarboxylic acid under hydrothermal conditions. The single-crystal X-ray structure reveals that 1 is a 2D bi-layered coordination polymer. Single-crystals are triclinic, space group P 1 , with a?=?7.065(3), b?=?7.812(4), c?=?9.031(4)?Å, α?=?75.568(8), β?=?68.970(8), γ?=?75.927(8)°, V?=?444.0(3)?ų, Z?=?2. Variable temperature magnetic susceptibility measurements demonstrate a ferromagnetic interaction in 1.     

Synthesis,crystal structure,thermal stability,and luminescent properties of lithium trimesate coordination polymer

Russian Chemical Bulletin - A metal-organic coordination polymer of the formula [Li3(btc)(H2O)] (1a) (H3btc is the trimesic acid, C6H3(COOH)3) was obtained upon heating a mixture of LiBH4 and H3btc...     

Novel 1D coordination polymer {Tm(Piv)3}n: Synthesis,structure, magnetic properties and thermal behavior

The new 1D coordination polymer {Tm(Piv)₃}_n (1), where Piv=OOCBu^t?, was synthesized in high yield (>95%) by the reaction of thulium acetate with pivalic acid in air at 100 °С. According to the X-ray diffraction data, the metal atoms in compound 1 are in an octahedral ligand environment unusual for lanthanides. The magnetic and luminescence properties of polymer 1, it’s the solid-phase thermal decomposition in air and under argon, and the thermal behavior in the temperature range of ?50…+50 °С were investigated. The vaporization process of complex 1 was studied by the Knudsen effusion method combined with mass-spectrometric analysis of the gas-phase composition in the temperature range of 570–680 K.     

Synthesis, structure, and thermal stability of a new 2D copper(II) coordination polymer based on 2-propyl-1H-imidazole-4,5-dicarboxylate

A new Cu(II) coordination polymer with singly deprotonated 2-propyl-imidazole-4,5-dicarboxylate (H₃PIDC) as bridging ligand of formula [Cu(H₂PIDC)₂] _n (I) was synthesized and characterized by IR, element analysis, and X-ray diffraction method. Compound I crystallizes in the monoclinic space group P2₁/n with cell parameters a = 8.332(1), b = 10.160(1), c = 11.228(1) Å, β = 91.13(1)°, V = 950.3(2) ų, M _r = 457.88, Z = 2, ρ _c = 1.600 g/cm³, F(000) = 470, μ = 1.202 mm^?1, R ₁ = 0.0412, and wR ₂ = 0.1064 for 2015 observed reflections. The Cu²⁺ ions are coordinated by four H₂PIDC^? ligands via N,O-chelating and O-bridging mode to form 2D layer planes, which are further linked by intermolecular hydrogen bonds and weak interactions into a 3D framework.     

Synthesis,characterization and NLO properties of a new 3D coordination polymer assembled from p-aminobenzoic acid

Reaction of Zn(NO₃)₂·6H₂O with p-aminobenzoic acid in a 1:2 molar ratio under ethanol medium at room temperature affords a new three dimensional (3D) coordination polymer [Zn(PABA)₂]·H₂O (1) (PABA = p-aminobenzoic acid). Single-crystal X-ray diffraction reveals that 1 crystallizes in the orthorhombic system, space group P2₁2₁2₁, a = 7.614(2), b = 11.133(3), c = 16.869(4). 1 adopts a 3D open framework with H₂O molecules in the cavities. PABA, acting as bridging ligand as well as coordinating ligand, adopts a different coordination mode to bridge Zn atoms and form the 3D supramolecular structure which is further stabilized by N–H?O, O–H?O hydrogen bonding and π–π stacking interactions. Powder second-harmonic generation (SHG) efficiency measurement with Nd:YAG laser (1064 nm) radiation shows that the SHG efficiency of 1 is equivalent to KDP crystal. The present work also demonstrates that the framework of 1 is retained after removal of the guest H₂O molecules, and the H₂O molecules can be reintroduced into the framework, indicating that this complex may also be used to generate porous materials.     

Synthesis,structure, and properties of a coordination polymer based on N- and O-donors

A ternary coordination polymer, [Cd(L)(pbda)_0.5] _n [HL?=?3,5-bis(2-pyridylmethyl)aminobenzoic acid, pbda?=?dianion of 1,4-benzenedicarboxylic acid], has been synthesized and characterized by elemental analysis, FT-IR spectroscopy, powder X-ray diffraction, thermogravimetric analysis, and single-crystal X-ray diffraction analysis. The single-crystal X-ray crystallography reveals that the complex is a 2-D wave-like network. The cadmium has an unsymmetrical seven-coordinate [CdN₂O₅] geometry, coordinated by two nitrogens and five oxygens from L^? and pbda. Hydrogen bonds between the uncoordinated (2-pyridylmethyl)amino groups from adjacent layers form dimers across the inversion center, superposing different layers to construct a 3-D framework. To the best of our knowledge, [Cd(L)(pbda)_0.5] _n represents the first example of a complex containing 3,5-bis(2-pyridylmethyl)aminobenzoate.     

Synthesis,molecular structure,photophysical properties and spectroscopic characterization of new 1D-magnesium(II) porphyrin-based coordination polymer

Research on Chemical Intermediates - Chemical preparation, X-ray diffraction, spectral and photophysical studies were performed for H2TPBP (5,10,15,20-tetrakis[4 (benzoyloxy)phenyl] porphyrin),...     

Synthesis,structures and adsorption properties of two new magnesium coordination polymers

Two new magnesium coordination polymers, [Mg(9,10-ADC)(H₂O)₂(DMF)₂]_n (1) and [Mg₆(1,4-NDC)₅(HCO₂)₄(DMF)(H₂O)]_n·2n[H₂N(CH₃)₂]·2n(DMF) (2) (9,10-ADC = 9,10-anthracenedicarboxylate; 1,4-NDC = 1,4-naphthalenedicarboxylate) have been solvothermally synthesized. Compound 1 displays a one-dimensional linear chain structure, which is orderly constructed from magnesium metal cations connecting with carboxylic oxygen atoms of 9,10-H₂ADC along the a axis. Compound 2 exhibits a three-dimensional framework composed of infinite chains of corner-sharing octahedral MgO₆ with 1,4-NDC ligands forming one-dimensional channels along the a axis, where guest molecules reside. When guest molecules are removed, no structural transformation is found to occur, generating a robust structure with permanent porosity. The studies of CO₂ absorption suggest that compound 2 is a promising adsorbent material for CO₂.     

Synthesis, structure, and properties of a new layered coordination polymer based on zinc(II) carboxylate

Heating of zinc(II) nitrate and 2,5-thiophenedicarboxylic acid (H₂Tdc) in the presence of hexamethylenetetramine in N-methylpyrrolidone (Nmp) gave the crystals of a layered coordination polymer [Zn₂(Nmp)₂(Tdc)₂] · 2Nmp · 0.5H₂O, which were studied by X-ray diffraction. The compound was characterized by IR spectroscopy, elemental and thermogravimetric analyses, and luminescence measurements.     

Crystal structure and fluorescent properties of a 2D cadmium coordination polymer

A new 2D cadmium(II) coordination polymer {[Cd(MBD)(L)]·(H₂O)₂} _n (1) (H₂MBD = 5-methoxycarbonyl-benzene-1,3-dicarboxylic acid, L = 1,3-bis(benzimidazol-l-yl)-2-propanol) is synthesized, in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during the synthesis. In the structure of complex 1, each cadmium center is octahedrally coordinated by four O atoms from three carboxylate groups and two N of distinct L ligands. A detailed structural analysis reveales that compound 1 exhibits a unique 2D binodal (3,5)-connected (4².6⁷.8)(4².6) topology structure. Furthermore, the 2D layer is extended into a 3D network through π-π stacking interactions. The solid-state fluorescence properties of 1 are investigated at room temperature.     

Synthesis,crystal structure and properties of a neodymium(III) coordination polymer of 1D chain structure based on typical plenary Keggin cluster

A 1D zigzag chain compound, [{Nd(NMP)₆}(PMo₁₂O₄₀)] _n , has been synthesized by reaction of α-H₃PMo₁₂O₄₀?·?nH₂O, Nd₂O₃ and NMP (NMP?=?N-methyl-2-pyrrolidone) in acetonitrile–water mixture, and characterized by elemental analysis, IR and UV spectra, and X-ray single crystal structural analysis. The crystal structure indicates that the title compound forms a one-dimensional zigzag chain built from alternating polyanions and cationic units through Mo–O_t–Nd–O_t–Mo links. In the compound, Nd³⁺ are eight-coordinate with a bicapped trigonal prism geometry of oxygen atoms, from six NMP molecules and two adjacent polyanions, and two terminal oxygen atoms of the polyanions occupying the caps. The powder ESR spectrum at 110?K of the title compound after being exposed to sunshine shows the signal of Mo⁵⁺, g?=?1.96. The CV shows that the title compound undergoes five two-electron reversible reductions and that [PMo₁₂O₄₀]^3? are active centers for electrochemical redox in solutions; cations have a small effect on electrochemical redox.     

Synthesis,structure and properties of a one-dimensional coordination polymer containing both dicyanamide and ethylenediamine

The nickel(II) complex [Ni(en)₂{N(CN)₂}]ClO₄ 1 (en?=?ethylenediamine) has been synthesized and its structure determined. The complex forms a one-dimensional chain structure via the bidentate bridging ligand dicyanamide. A two-dimensional network is formed via interchain hydrogen-bond interactions. The magnetic properties of the compound (5–300?K) show the existence of weak antiferromagnetic exchange interactions between paramagnetic centers along chains.     

Sonochemical synthesis of a new nano-scale 1D copper organic coordination polymer; thermal and spectroscopic characterizations

Single crystal of a new one-dimensional copper organic coordination polymer, 1D-CuOCP, [Cu(HL)NO₃]_n (1) Miyasaka, H., Saitoh, A., Abe, S. (2007) Coord. Chem. Rev., 251(21): 2622–2664.[Crossref], [Web of Science ®] , [Google Scholar] (H₂L = [2-[1-(2-hydroxy-propylimino)-ethyl]-phenol]) and its nanostructure, have been synthesized by slow evaporation of methanol solution of compound (1) Miyasaka, H., Saitoh, A., Abe, S. (2007) Coord. Chem. Rev., 251(21): 2622–2664.[Crossref], [Web of Science ®] , [Google Scholar] and sonochemical process respectively. Nanostructure of the complex was characterized by X-ray powder diffraction (XRD), FT-IR spectroscopy and scanning electron microscopy (SEM) and the structure of compound 1 was determined by single-crystal X-ray diffraction. Thermal stability of compound 1 in its nanosize form has also been studied by thermal gravimetric analysis (TGA). The effect of concentration of initial reagents on size and morphology of nanostructured compound 1 has been examined. The brightness of this study is to use the nanostructure of 1D-CuOCP as precursor to prepare single phase CuO nanoparticles via a solid-state decomposition procedure. Characterization methods confirmed that CuO nanoparticles with an average diameter of 40 nm were obtained from direct calcination of the precursor at 500°C under air.     

Photocatalytic properties and luminescent sensing of a new 2D layer coordination polymer

A 2D coordination polymer [Zn2(betc)(bip)2]·3H2O (1) has been synthesised by deploying mixed ligand strategy . The photoluminescence properties of 1 in different solvents have been investigated and its sensing properties to detect nitroaromatic compounds (NACs) have been explored. 1 displayed selective sensing for 4- nitrotoluene (4-NT) with lower limit of detection (LOD) 0.62 ppm. The probable mechanism for sensing of NACs by 1 ha s been addressed using quantum chemical calculations. Also photocatalytic properties of 1 to photo-decompose model aromatic dyes viz. methyl violet (MV) and 20 rhodamine B (Rh B) have been evaluated. The experiments indicated that 1 displayed better photocatalytic performance in photo-degrading MV than Rh B. The plausible mechanism through which 1 displayed photocatalytic degradation of aromatic dyes had been revealed using density of states (DOS) and partial DOS calculations.

The probable mechanism for the photocatalytic property and emission quenching of 1 has been proposed with the aid of density of states and partial density of states calculations.     

Crystal structure,thermal and fluorescent properties of a 1D Cd(II) coordination polymer based on the bis(benzimidazole) ligand

A 1D cadmium (II) coordination polymer {[Cd₂(L)₃Cl₃]·Cl} _n (1) (L = 1,3-bis(benzimidazol-l-yl)-2-propanol) is synthesized by the hydrothermal reaction and characterized by elemental analysis, IR, TG, and X-ray single crystal diffraction. Compound 1 crystallizes in the hexagonal system, space group P63/m with a = 15.4857(11) Å, b = 15.4857(11) Å, c = 14.478(2) Å, γ = 120°, V = 3006.8(5) ų, Z = 2. In the structure of complex 1, each cadmium center is hexahedrally coordinated by three chlorine atoms and three nitrogen atoms of three distinct L ligands. A detailed analysis reveals that compound 1 exhibits a 1D chain of beads and the adjacent chains are further linked by C-H…Cl hydrogen bonding to form a 2D supramolecular framework. Furthermore, the solid-state fluorescent property of 1 is investigated at room temperature.     

Synthesis,structure and characterization of new 1D and 2D Ni(II) coordination polymers

Two new Ni(II) coordination polymers, namely [Ni₃(Hsdac)₂(sdac)₂(2,2′-bipy)₂] (1) and [Ni₂(sdac)₂(4,4′-bipy)₂]·2H₂O (2) (sdba = 4,4′-sulfonyldibenzoate, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), have been prepared under hydrothermal conditions and characterized by single crystal X-ray diffraction analyses. Compound 1 possesses an interesting chain structure. Adjacent chains are further linked through H-bond interactions between Hsdac ligands to give a two-dimensional (2D) supramolecular architecture. Compound 2 displays an unusual 2D polyrotaxane-like network.     

First coordination polymer based on diterpenoids. Synthesis,structure, and magnetic properties

Russian Chemical Bulletin - One-dimensional coordination polymer was obtained by cation exchange reaction of triethylammonium salt of methyl ent-16α-H-phosphonyloxybeyeran-19-oate with CuCl2....     

Nonlinear optical material of a low-dimensional coordination polymer: Synthesis, structure, NLO and fluorescence properties

Employing unsymmetrical 2-mercapto-5-methyl-1,3,4-thiadiazole and 2,2′-bipyridine as mixed ligands, a new low-dimensional coordination polymer [Zn(MMTA) 2 (2,2′-bipy)] n (MMTA = 2-mercapto-5-methyl-1,3,4-thiadiazole, 2,2′-bipy = 2,2′-bipyridine), has been synthesized under solvothermal condition and characterized by single crystal X-ray diffraction. This compound crys- tallizes in the noncentrosymmetric space group Cc, with cell parameters: a = 8.291(4) , b = 15.483(9) , c = 15.620(6) , = 96.00(5)°, V = 1994.1(2) 3 , and Z = 4. The mixed ligands link the zinc center into a mononuclear unit, which is futher linked by weak C-H···N and C-H···S hydrogen bonds into a three-dimensional noncentrosymmetric framework. The compound exhibits intense photoluminescence and distinct NLO properties at room temperature. The intensity of the green light produced by the powder sample of the compound is about 3.2 times that produced by KDP powder. On the basis of the results of TG analysis, the structure is thermally stable up to ～260 °C.