Dimensional Coordination Polymer Research Articles

Synthesis, structure and topological analysis of a novel three dimensional Co(II) coordination polymer constructed by an unsymmetrical ligand

Through in situ basic hydrolysis of cyanide functional group of 3-(1H-benzo[d]imidazol-1-yl)-5-(1H-imidazol-1-yl)benzonitrile a new three dimensional porous coordination polymer {[Co2(BIIBA)3]·(NO3)·5H2O}n (1) (BIIBA=3-(1H-benzo[d]imidazol-1-yl)-5-(1H-imidazol-1-yl)benzoate) have been isolated under hydrothermal conditions and characterized by single crystal X-ray diffraction. Topological analysis of 1 revealed a (3,3,4,5)-connected 4-nodal unprecedented pkb8 net with point symbol {4.62}2{42.66.82}{63}{65.8}.

Proton Conduction in a Nonporous One Dimensional Coordination Polymer

Complex impedance measurements on single crystals and pellets of a CuCo-orotate coordination polymer, as a function of relative humidity and temperature, reveal proton conduction with a relatively high thermal activation energy, a negligible isotope effect, a large pre-exponential factor in the conductivity model, and a strong dependence on humidity, all of which are consistent with a vehicle mechanism. The proton conductivity found for this polymer compares favorably with that of MOFs and related porous materials even though it has no framework with pores and channels to provide proton-conduction pathways.

Cationic zinc (II) dimers and one dimensional coordination polymer from ionic carboxylic acid

A rare example of chelating two tetra cationic paddle-wheel zinc dimers were synthesized from the reaction between flexible imidazolium carboxylate (L H 2 B r 2 ) and corresponding zinc precursors. A zinc coordination polymer was synthesised by treating in situ generation of 2 in the presence of 4,4’-bipyridine. These new molecules, dimers and polymer, were characterized by FT-IR, NMR, UV-vis, fluorescent and single crystal X-ray diffraction techniques. Zinc polymer is the first example of 1D coordination polymer constructed by tetra cationic zinc dimer as a secondary building unit in coordination polymer. Tetra cationic paddle-wheel zinc dimers and zinc coordination polymer were synthesized and structurally characterized from the reaction between flexible imidazolium carboxylate and corresponding zinc precursors.

Study of a 2D coordination polymer of Zn(II) with 5-aminoisophtalic as ligand.

The design, synthesis and characterization of infinite one-, two- and three dimensional coordination polymers have attracted increasing attention in chemistry and material science research due to their potential applications as drug deliver, magnetic and optical sensors [1]. In particular, a series metal-organic frameworks MOFs - (a coordination polymer subclass) with different topological nets such as honey-comb, brick wall, ladder, herringbone, diamondoid and rectangular grids have been comprehensively discussed by Yaghi, Kitagawa and their co-workers [2] and it was observed that the type of metal ion and organic bridge ligand determines the dimensionality and the topology of the network. In this work we report a new 2D coordination polymer obtained by from ZnSO4.7H2O and 5-aminoisophtalic acid (5AIF), using the base diffusion method (DMSO as solvent). The crystal structure was determined from single crystal X-ray diffraction data collect in a Gemini-Oxford diffractometer. The Zn atom is tetrahedrally coordinated with two oxygen and one nitrogen from three different 5AIF molecules and one oxygen from DMSO molecules. The molecular packing indicates the formation of a 2D parallel to (010) forming hydrophilic cavities along [001]. The 2D network is stabilized by intermolecular hydrogen bonds involving the donor hydroxyl group (O3-H3) and the acceptor nitrogen atom (N1). The geometrical features of this new 2D coordination polymer were are all in agreement with similar fragments deposited in CSD [3].

Cadmium coordination polymers based on flexible bis(imidazole) ligands: A rare example for doublet of doublet cadmium polyhedron arrangements

Two one-dimensional (1D) coordination polymers, [{LCd(O2NO)2(DMF)2}2{(LCd(O2NO)2(DMF))(DMF)}2]n (1) and [L′Cd(O2NO)(ONO2)(DMF)2]n (2), having an aryl chromophoric unit and a flexible bis(imidazole) tail, 9,10-bis{(benzimidazol)methyl}anthracene (L) and 1,4-bis{(imidazol)methyl}benzene (L′), with various coordination modes have been obtained. Molecule 1 represents the first structurally characterized one dimensional coordination polymer consisting of both hepta- and octa-coordinated cadmium centers. In 1, two distorted pentagonal bipyramidal Cd(II) centers and two distorted triangular dodecahedral Cd(II) centers are alternately arranged via bridging bidentate N,N-chelating ligand, L. Whereas, a distorted pentagonal bipyramidal Cd(II) center is formed in 2 where the sterically less crowded L′ serves as a bridging bidentate N,N-chelating ligand. Furthermore, 1 and 2 have been characterized by elemental analysis, FT-IR, 1H NMR, UV–vis and fluorescent techniques.

Syntheses and catalytic oxidation of tetrameric and polymeric copper(II) 1,3-propanediaminetetraacetates

Tetranuclear copper dihydrogen 1,3-propanediaminetetraacetate [Cu4Cl4(1,3-H2pdta)2] (1) was obtained from an acidic solution, which was converted to one dimensional coordination polymer [Cu(1,3-H2pdta)]n (2) and its hydrated derivative [Cu4(1,3-pdta)2(H2O)4]·H2O (3) respectively (H4pdta=1,3-propanediaminetetraacetic acid, C11H18N2O8) under heating condition. The four copper ions in 1 and 3 exist in quasi-symmetrical tetrahedral environments. Complex 1 consists of a tetrameric neutral unit [Cu4Cl4(H2pdta)2], which extents into a 3D supramolecular structure by inter-molecular hydrogen bonds [O3⋯Cl(1) 3.155(6)Å]. In 2, [1,3-H2pdta]2− ligand links each copper ion to generate a neutral polymeric chain [Cu(1,3-H2pdta)]n with strong intra-molecular hydrogen bonds [O4⋯O2 2.620(7)Å]. The protonated carboxy groups in 1 and 2 show weak coordination, while deprotonated nitrogen atoms are in coordination mode. All of the three complexes show catalytic activities to the conversions of cyclohexane to cyclohexanol and cyclohexanone with hydrogen peroxide in solution. This is attributed to the nano-constructed copper species (∼1.0nm) and the copper coordination polymer. The chloride ion seems not related to the conversion, while unsaturated configuration is considered favorably for the conversion.

Different dimensional coordination polymers with 4,4׳-oxybis(benzoate): Syntheses, structures and properties

Five transition-metal coordination polymers, namely, [Zn7Cl6(oba)4]n (1), [Cd7Cl6(oba)4]n (2), [Zn(oba)(H2O)]n (3), [Ag2(oba)]n (4) and [Co(oba)(H2O)2]n (5) (H2oba=4,4′-oxydibenzoic acid), have been achieved under hydrothermal conditions and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. The X-ray single-crystal diffraction reveals that compounds 1 and 2 are isomorphism, featuring pillared-layer 3D motifs, in which the 2D inorganic layers (Zn6Cl7)n (or (Cd6Cl7)n) are connected by oba2− pillars. Compound 3 exhibits 1D stair-like chain and extends to a 3D network by two different interchain O–H–O hydrogen bonding interactions while compound 4 features wave chains and stretches to 2D layer by interchain Ag–O weak contacts. Compound 5 shows 2D network in which Co-chains are pillared by oba2− ligand and then forms a 3D network by four different O–H–O hydrogen bonding interactions. Furthermore, 1–4 exhibit luminescent properties at a solid state and 5 shows antiferromagnetic behavior.

Novel 1D Mn(II) complexes containing aromatic dicarboxylic acids

Three Mn(II) complexes of [MnL(Bipy)(H2O)] n (I), [Mn3(Phen)2(HL)2(L)2]n (II), and [Mn(Phen)2(HL)(OH)] (III), where L = 4,4′-(2-acetylpropane-1,3-diyl)dibenzoic acid, Bipy = 2,2′-bipyridine, and Phen = 1,10-phenanthroline, were hydrothermally synthesized and characterized by single crystal X-ray diffractions, infrared spectroscopy, thermogravimetric analyses, and magnetic analyses. Complexes I and II are one dimensional (1D) coordination polymers which can form the supramolecules with the help of the intermolecular hydrogen bond interactions. Finally, the lande factors are simulated by magentochemical analysis to be 2.15 and 1.80 for I and II with S = 5/2, respectively.

A Manganese(II) Coordination Polymer with the Ligands ­Azide and Picolinate: Synthesis, Structure, and Magnetic Properties

AbstractThe two dimensional MnII coordination polymer [Mn3(pic)2(N3)4(CH3OH)]n (1) with the ligands azide and picolinic acid (Hpic) was synthesized and characterized by IR spectroscopy, elemental analysis, and powder and single‐crystal X‐ray diffraction analysis. Meanwhile, analysis of the magnetic properties revealed antiferromagnetic exchange for polymer 1.

Functionalized oxathiacrown macrocycles: Synthesis, characterization and coordination to palladium(II), ruthenium(II) and copper(I)

New oxathiacrown macrocycles with exocyclic double bond 1 and 2 were synthesized and characterized. Their coordination behavior with soft transition metals is investigated. Reaction of 1 with PdCl2 afforded exo-coordinated complex 3 with the two S-donor atoms. With RuCl2(PPh3)3, the macrocyclic ligand 1 is bonded through three donor atoms (two sulfur and one oxygen) to the ruthenium center in a facial coordination mode. By contrast, double and single-stranded one dimensional (1D) coordination polymers were obtained by reaction of CuBr with macrocycles 1 and 2. All complexes were spectroscopically characterized and their structure was secured by X-ray diffraction analysis.

Slow magnetic relaxation in lanthanide ladder type coordination polymers

A series of four isostructural lanthanide-containing one dimensional coordination polymers with picolinic (pic) and glutaric (glu) acids, Ln(glu)(pic)(H2O)2, where Ln = Gd(III) (1), Tb(III) (2), Dy(III) (3) and Er(III) (4) were synthesized under hydrothermal conditions and structurally characterized by powder and single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric measurements. These compounds are isostructural to the previously reported Sm(glu)(pic)(H2O)2 and the structure consists in pairs of lanthanide ions double bridged by carboxylic groups which are connected along c by the glutaric acid ligands as a ladder type 1D coordination polymer. The magnetic properties of these compounds were studied by static magnetization and AC magnetic susceptibility measurements in the temperature range 1.7-300 K. Weak dominant ferromagnetic interactions between lanthanide cations were found in the compounds, except in compound 3. Compounds 1, 3 and 4 reveal frequency dependent AC susceptibility and slow relaxation of the magnetization under applied external static field. These data classify the Gd(III), Dy(III) and Er(III) compounds as molecular magnets. In spite of the ladder chain structure of the compounds this magnetic behaviour is not due to a single chain but instead it is ascribed to single ion anisotropic effects in the case of 3 and 4 and possibly to a phonon-bottleneck effect of the spin-lattice relaxation in 1.

Two dimensional coordination polymers with 3,3′-thiodipropionate: An unprecedented coordination mode and strong hydrogen-bond network

Four novel coordination polymers, namely [Co(μ3-tdp)(ina)2]n (1), [Cu(μ3-tdp)(ina)2]n (2), [Zn(μ3-tdp)(ina)2]n (3) and [Zn(μ3-tdp)(na)2]n (4) [tdp: 3,3′-thiodipropionate, ina: isonicotinamide and na: nicotinamide], were synthesized and structurally characterized by elemental analysis, IR and single-crystal X-ray diffraction techniques. Each M(II) ion (M(II)Co(II) in 1, Cu(II) in 2, Zn(II) in 3 and Zn(II) in 4) is coordinated by two nitrogen atoms of two different pyridine rings and four oxygen atoms from three different tdp ligands, forming distorted octahedral geometries. The tdp ligand exhibits an unprecedented coordination mode, namely the μ3-κO,O′:κO″:κO″′-bridging mode. Single crystal X-ray diffraction analysis results demonstrated that complexes 1–4 exhibit 2D layers with a point symbol of 33·43·54, which are extended into 3D supramolecular frameworks by R22(8) hydrogen-bonding motifs. Thermal analysis results showed that 2D complexes are stable up to 225, 189, 196 and 162°C, respectively. Moreover, the photoluminescent properties of complexes 3 and 4 were investigated at room temperature.

Syntheses and structures of three heterometallic coordination polymers derived from 4-pyridin-3-yl-benzoic acid

Three lanthanide–transition-metal coordination polymers, namely, [Er2L6(H2O)][Cu2I2] (1), [ErL3][CuI] (2), and [Dy2L6(BPDC)0.5(H2O)4][Cu3I2] (3) (HL=4-pyridin-3-yl-benzoic acid, H2BPDC=4,4′-biphenyldicarboxylic acid) have been made by reacting Ln2O3 and CuI with HL at different temperatures under hydrothermal conditions. All the complexes are characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction, respectively. 1–3 all construct from dimeric {Ln2} and {Cu2} units and exhibit two types of the structural features: 1 is a two-dimensional layer, 2–3 are three-dimensional frameworks. Interestingly, the in situ formation of the BPDC ligand is found in the structure of 3. The distinct architectures of these complexes indicated that the reaction temperature plays an important role in the formation of higher dimensional coordination polymers.

Structural Variations in Coordination Polymers of Sodium and Cesium Dicarboxylates

The coordination polymer {[Na2L(μ-H2O)(H2O)3]·H2O}n (1) derived from 2,2′-(phenylmethylidene-bis(3,5-methyl-2-phenyleneoxy)] diacetic acid (H2L) has repeat units comprising of hexa-coordinate diaqua-bridged dinuclear sodium complex ions. These units are connected through intervening mononuclear complex parts having penta-coordinated sodium ions. The sodium ions adopt repeated hexameric chair-like arrangement in the polymer. The cesium salt of H2L namely [Cs(HL)(μ-H2O)(H2O)]n (2) is a coordination polymer. In this case one acid group of the ligand is deprotonated and 2 form self-assembly by intermolecular hydrogen bonds between the free carboxylic acid groups. The fluoro-substituted ligand 2,2′-(2-fluorophenylmethyledene-bis(3,5-methyl-2-phenyleneoxy)] diacetic acid (H2Lf) forms disodium salt with a composition [{Na2Lf(μ-H2O)(H2O)3}·H2O]n (3); which is a two dimensional coordination polymer. On the other hand the corresponding cesium salt of H2Lf has a composition [{(H2O)Cs(μ-H2O)(μ-Lf)Cs(H2O)2}] (4); which is also a 2-D coordination polymer. The cesium ions are six or nine coordinate in the polymer and the coordination polymer possesses unusual Cs···F–C coordination bond.

Quantitative estimation of the antiferromagnetic interaction between Cu(II) and Sm(III) in two dimensional heterometallic coordination polymer with isonicotinic acid as tectons

Abstract The syntheses, structure and magnetic property of a novel two dimensional 3d–4f coordination polymer 2∞[CuSmL(NO3)2(IN)], 1 (L2− = N, N′- propylenedi (3-ehoxysalicylideneiminato), the dianion of the Schiff base obtained from the 2:1 condensation of 3-ethoxysalicylaldehyde with 1,3-propanediamine, IN− = the isonicotinate ion) has been reported. The heterobinuclear units are connected through exo-bidentate ligands IN−, leading to an extended 2D structure. A fit of the magnetic susceptibility data yields gCu = 2.109, gSm = 0.476, JCuSm = − 0.893 cm− 1, θ = − 3.37 K, and TIP = 0.001257 emu K mol− 1 with a good discrepancy factor of Rχ = 4.4 × 10− 5. This is the first quantitative estimation of the strength of the antiferromagnetic interaction between Cu(II) and Sm(III) ions to the best of our knowledge.

Synthesis, crystal structure and luminescence properties of lanthanide coordination polymers with a new semirigid bridging thenylsalicylamide ligand

Two new lanthanide coordination polymers based on a semirigid bridging thenylsalicylamide ligand ([Ln{sub 2}L{sub 3}(NO{sub 3}){sub 6}]·(C{sub 4}H{sub 8}O{sub 2}){sub 2}){sub ∞} were obtained and characterized by elemental analysis, X-ray diffraction, IR and TGA measurements. The two compounds are isostructure and possess one dimensional trapezoid ladder-like chain built up from the connection of isolated LnO{sub 3}(NO{sub 3}){sub 3} polyhedra (distorted monocapped antisquare prism) through the ligand. The photoluminescence analysis suggest that there is an efficient ligand-to-Ln(III) energy transfer in Tb(III) complex and the ligand is an efficient “antenna” for Tb(III). From a more general perspective, the results demonstrated herein provide the possibility of controlling the formation of the desired lanthanide coordination structure to enrich the crystal engineering strategy and enlarge the arsenal for developing excellent luminescent lanthanide coordination polymers. - Graphical abstract: We present herein one dimensional lanthanide coordination polymers of a new semirigid exo-bidentate ligand which not only display interesting structures but also possess strong luminescence properties. Display Omitted - Highlights: • We present lanthanide coordination polymers of a new semirigid exo-bidentate ligand. • The lanthanide coordination polymers exhibit interesting structures. • The luminescent properties of Tb(III) complexes are discussed in detail.

A two-dimensional metal organic network with 1,3,5-benzenetricarboxylate and cobalt (II) ions: synthesis, structure and topology

We herein report the synthesis and structure of a two dimensional (2D) metal-organic coordination polymer (or metal-organic network) which extends in two dimensions via Co2+ and 1,3,5-benzenetricarboxylate ions. The hydrothermal reaction of (2R,2′R,2″R)-2,2′,2″-(benzenetricarbonyltris(azanediyl))tripropanoic acid (parent ligand) with cobalt nitrate in the presence of pyridine lead to the decomposition of the parent ligand producing 1,3,5-benzenetricarboxylate, which in turn reacted with cobalt ions to afford a 2D network [Co1.5(BTC3–)·(pyridine)3·(H2O)](H2O)0.26·(MeOH) (1). This network was characterized by single crystal X-ray diffraction and IR spectroscopy. The topological study indicated that the framework is a 3,4-connected binodal net.

One dimensional coordination polymer of cadmium(II) with thiocyanate bridge : synthesis, characterization and molecular properties

One dimensional coordination polymer of cadmium(II) with thiocyanate bridge : synthesis, characterization and molecular properties

Two new dysprosium–organic frameworks contaning rigid dicarboxylate ligands: Synthesis and effect of solvents on the luminescent properties

Two new two–dimensional (2D) dysprosium coordination polymers [Dy(2,4′-bpdc)(DMF)2(NO3)]n (1) and {[Dy(2,4′–bpdc)(1,4-BDC)0.5(DMF)(H2O)]1.5H2O}n (2) (2,4′-H2bpdc=2,4′–biphenyldicarboxylic acid, 1,4-H2BDC=1,4–benzenedicarboxylic acid, DMF=N,N′-dimethylformamide) were synthesized under solvothermal condition and stucturally characterized by means of single-crystal X-ray diffraction, IR spectroscopy, and elemental analysis. Single-crystal X-ray analysis revealed that the two coordination polymers possess two types of 2D layered structures. From the viewpoint of network topology, the structures of 1 and 2 can be simplified as (4,4) network. We discuss the effect of solvents and temperature on luminescence properties. The fluorescence spectra of 1 at room temperature and 77K in the solid-state are almost the same, except the stronger emission intensities derived from ligand–centered at 77K. It is because the quenching by O3H oscillators was protected at low temperature. Coordination polymer 2 displays characteristic Dy3+ ion yellow–green luminescence under 290nm excitation in DMSO (dimethyl sulfoxide), CH3CN, and CH3OH solvents. The fluorescence intensities of 2 increased in the order of DMSO>CH3CN>CH3OH. We also studied the fluorescence lifetimes of 1 and 2, and the results revealed that the lifetime in DMSO solvent at room temperature reached to 9.53μs. Compared with the dysprosium coordination polymers, coordination polymer 2 presents a longer lifetime. Additionally, we calculate the triplet state T1 datum from the emission spectrum of the Gd3+ coordination polymer and discuss the energy transfer mechanisms. The energy transfer process from the lowest triplet state energy level of 2,4′-H2bpdc ligand to the 4F9/2 state energy level of Dy3+ ion is inefficient for both 1 and 2. The energy transfer process is effective after we introducing the chelating ligand 1,4-H2BDC to the construct of coordination polymer 2, which is ascribe to 1,4-H2BDC may participate in the process of energy transfer.

Novel magnetic CoII complexes: Synthesis and characterization

Abstract Two CoII complexes of [Co(phen)2(H2O)(HL)OH] (1) and [Co(bpy)(H2O)(EtOH)L]n (2), where L = 4,4′-(2-acetylpropane-1,3-diyl)dibenzoic acid, phen = 1,10-phenanthroline and bpy = 2,2′-bipyridine, were hydrothermally synthesized and characterized by the single crystal X-ray diffractions, the infrared spectroscopy, the thermogravimetric analyses, and the magnetochemical analyses. Complex 2 can form one dimensional coordination polymers with the help of bridge ligand of L2 −. Furthermore, both 1 and 2 can form the supramolecules through the intermolecular hydrogen bond interactions. The higher values of Tχm, 3.29 K · cm3/mol (g = 2.65, S = 3/2) at 300 K, reveal that there should be typical contribution of the orbital momentum for the 4T1g ground state of the CoII ions in complex 1.