Structure Of Coordination Polymer Research Articles

Synthesis, structure, and property of a two-dimensional layer coordination polymer on Ag(I)

ABSTRACTBy hydrothermal method, a new coordination polymer [Ag3(btc)(dmt)(H2O)]n (1) (H3btc = 1,3,5-benzenetricarboxylic acid, dmt = 2,4-diamino-6-methyl-1,3,5-triazine), has been synthesized and structurally characterized by IR spectrum, X-ray single diffraction, and elemental analysis. Compound 1 exhibits a planar 2D layer with 2-nodal (3,4)-connected {4.62}4{64.102} topology and further extends to 3D framework through hydrogen bond and Ag…O weak interactions. Moreover, compound 1 displays luminescent property at solid state and holds good catalytic activity toward photocatalytic degradation of RhB.

Multiresponsive Adenine-Based Luminescent Zn(II) Coordination Polymer for Detection of Hg2+ and Trinitrophenol in Aqueous Media

The present work reports the synthesis, characterization, and crystal structure of a neutral two-dimensional adenine-based luminescent coordination polymer (LCP) with Zn(II) metal nodes. The photoluminescence property of the d10 LCP [Zn(μ2-1H-ade)(μ2-SO4)] (1) has been exploited to use 1 as a dual detection probe for the selective sensing of Hg2+ and 2,4,6-trinitrophenol (TNP) in the aqueous phase from among a variety of cations and a pool of aromatic nitro compounds, respectively. Competitive fluorometric experiments involving a series of cation combinations or mixture of nitro compounds established 1 as an efficient and selective sensor for Hg2+ and TNP in aqueous solutions. The limits of detection for sensing of Hg2+ and TNP in aqueous solutions using LCP 1 are 70 and 0.4 nM, respectively. For in-field sensing applications, 1-coated test paper strips have been developed. They show luminescence upon exposure to UV radiation, and the luminescence intensity is quenched upon addition to aqueous solutions o...

Anhydrous, Homoleptic Lanthanide Frameworks with the Pentafluoroethyltricyanoborate Anion.

Pentafluoroethyltricyanoborate frameworks of rare-earth metal ions of the general formula [Ln{C2F5B(CN)3}3(OH2)n] (Ln = La, Eu, Ho; n = 0, 3; [Ln13(OH2)n]) were synthesized using the oxonium salt (H3O)[C2F5B(CN)3] ((H3O)1) and lanthanide chlorides LnCl3·nH2O as starting compounds. Single-crystals of ∞3[La{C2F5B(CN)3}3] (∞3[La13]) are obtained from the room temperature ionic liquid (RTIL) [EMIm]1 using either a ionothermal approach or by recrystallization of anhydrous microcrystalline [La13] that is obtained from reactions in aqueous media after drying in a vacuum. Removal of water from [Ln13(OH2)3] (Ln = Eu, Ho) to give microcrystalline ∞3[Ln13] is achieved in a vacuum at elevated temperatures. All compounds were characterized by vibrational and NMR spectroscopy, thermogravimetry, and elemental analysis. The structures of the three-dimensional coordination polymers ∞3[Eu13(OH2)3] and ∞3[La13] were elucidated by single-crystal X-ray-diffraction. According to powder diffraction studies on anhydrous ∞3[Ln13] (Ln = La, Eu, Ho), the three compounds are isotypic. A study of the photoluminescence properties reveals that both Eu3+ compounds, [Eu13] and [Eu13(OH2)3], are strongly luminescent, the emission of the anhydrous framework being significantly more intense than the one of the hydrate. The Eu-compounds benefit from a sensitizer effect of the anion. In contrast, the Ho-containing framework ∞3[Ho13] exhibits separate chromophores and a strong reabsorption of the fluorescence by the Ho3+ ions.

A New Copper(I) Complex Based on 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole: Synthesis, Crystal Structure, Theoretical Study, Thermal Behavior and Luminescence

The synthesis, characterization and structure of a 1D coordination polymer {[CuBr(3-abpt)] ⋅2DMSO} n (1) (3-abpt = 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole) is described. X-ray structural analyses reveal that 1 exhibits a 1D ladder-like chain structure and each copper(I) center in 1 displays a distorted tetrahedral coordination geometry {CuN 3Br}. Density functional theory and time-dependent density functional theory calculations at the B3LYP/LanL2DZf + 6-31G* level were performed on complex 1 to rationalize its experimental absorption spectra. The luminescent property and thermal behavior of the complex were also investigated. The synthesis and structural characterization of a new luminous copper(I) complex, namely, {[CuBr(3-abpt)]×2DMSO}n (3-abpt = 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole) is reported. The Cu1 and Cu1A are connected by two 3-abpt ligands to form a 12-membered ring and the distance between the two Cu atoms is 5.464(1) Å.

Self-assembly and crystal structures of coordination polymers constructed by 4′-hydroxyisoflavone-3′-sulfonates with Cs(I) and Rb(I)

Four coordination polymers, [CsL1(H2O)2]·H2O (1), [CsL2(H2O)2]·H2O (2), [Rb2(L2)2(H2O)2]·2H2O (3) and [RbL3(H2O)] (4), were synthesized by Cs(I), Rb(I) and 4′-hydroxyisoflavone-3′-sulfonates L1–L3 [L1 = 7-methoxy-4′-hydroxyisoflavone-3′-sulfonate, L2 = 7-ethoxy-4′-hydroxyisoflavone-3′-sulfonate, L3 = 7-ethoxy-4′,5-dihydroxyisoflavone-3′-sulfonate]. The crystal structures of 1–4 were determined by single-crystal X-ray diffraction. The influences of 4′-hydroxyisoflavone-3′-sulfonate ligands and Cs+, Rb+ on their structural features and self-assembly were investigated. The sulfonates of L1–L3 not only coordinate with Cs+ or Rb+ directly, but also bridge the organic region and the inorganic region in 1–4. Non-covalent interactions such as coordination interaction, π–π stacking interaction and hydrogen bonding assembled 1–4 into 3-D networks together with the electrostatic interactions between Cs+, Rb+ and the sulfonate anions.

Synthesis, crystal structure, luminescent and magnetic properties of lanthanide coordination polymers based on a zwitterionic polycarboxylate ligand

A series of isostructural lanthanide coordination polymers (Ln-CPs) {[Ln(Cbdcp)·3H2O]·Cl·xH2O} Ln=Tb (1), Eu (2), Dy (3), Cbdcp=N-(4-carboxybenzyl)-(3,5-dicarboxyl)pyridinium, have been successfully synthesized and fully characterized. Complex 1 utilized as a representative chemosensor has the potential to serve as the first example of a luminescent Ln-CP material based on the zwitterionic type of organic ligand for selective and recyclable sensing of TNP in ethanol solution. Besides, Complex 3 has antiferromagnetic property and exhibits slow magnetic relaxation.

Crystal structures and hydrogen bonding in the isotypic series of hydrated alkali metal (K, Rb and Cs) complexes with 4-amino-phenyl-arsonic acid.

The structures of the alkali metal (K, Rb and Cs) complex salts with 4-amino-phenyl-arsonic acid (p-arsanilic acid) manifest an isotypic series with the general formula [M2(C6H7AsNO3)2(H2O)3], with M = K {poly[di-μ3-4-amino-phenyl-arsonato-tri-μ2-aqua-dipotassium], [K2(C6H7AsNO3)2(H2O)3], (I)}, Rb {poly[di-μ3-4-amino-phenyl-arsonato-tri-μ2-aqua-dirubidium], [Rb2(C6H7AsNO3)2(H2O)3], (II)}, and Cs {poly[di-μ3-4-amino-phenyl-arsonato-tri-μ2-aqua-dirubidium], [Cs2(C6H7AsNO3)2(H2O)3], (III)}, in which the repeating structural units lie across crystallographic mirror planes containing two independent and different metal cations and a bridging water mol-ecule, with the two hydrogen p-arsanilate ligands and the second water mol-ecule lying outside the mirror plane. The bonding about the two metal cations in all complexes is similar, one five-coordinate, the other progressing from five-coordinate in (I) to eight-coordinate in both (II) and (III), with overall M-O bond-length ranges of 2.694 (5)-3.009 (7) (K), 2.818 (4)-3.246 (4) (Rb) and 2.961 (9)-3.400 (10) Å (Cs). The additional three bonds in (II) and (III) are the result of inter-metal bridging through the water ligands. Two-dimensional coordination polymeric structures with the layers lying parallel to (100) are generated through a number of bridging bonds involving the water mol-ecules (including hydrogen-bonding inter-actions), as well as through the arsanilate O atoms. These layers are linked across [100] through amine N-H⋯O hydrogen bonds to arsonate and water O-atom acceptors, giving overall three-dimensional network structures.

Design and synthesis of coordination polymers with chelated units and their application in nanomaterials science

The advances and problems associated with the preparation, properties and structure of coordination polymers with chelated units are presented and assessed.

Structure of glutarate-containing uranyl coordination polymers with organic amides

Three new uranyl complexes [UO2(C5H6O4)(Meur)] (I), [UO2(C5H6O4)(Aa)] (II), and [(UO2)2(C5H6O4)2(Tmur)2(H2O)] • H2O (III), where C5H6O4 2− is glutarate anion, Meur is methylcarmamide, Aa is acetamide, and Tmur is tetramethylcarbamide, have been synthesized and characterized by X-ray diffraction. 1D uranyl-glutarate complexes have been found in the structures of all compounds; in I and II their composition is [UO2(C5H6O4)(L)] and crystallographic formula is AQ21M1 (where A = UO2 2+, Q21 = C5H6O4 2-, and M1 = L = Meur or Aa). In crystals III, chain complexes have the composition [(UO2)2(C5H6O4)2(Tmur)2(H2O)] and crystallographic formula A2Q2 02M3 1 (where A = UO2 2+, Q02 = C5H4O6 2-, and M1 = Tmur or H2O). All compounds were characterized by IR spectroscopy. Structural features of all known complexes of uranyl glutarate with neutral ligands have been discussed.

4-Cyanopyridine, a versatile mono- and bidentate ligand. Crystal structures of related coordination polymers determined by X-ray powder diffraction

4-Cyanopyridine (4-CNpy) as a monodentate ligand in single or double chains or as a bidentate ligand in two-dimensional networks.

CdO-NPs; synthesis from 1D new nano Cd coordination polymer, characterization and application as anti-cancer drug for reducing the viability of cancer cells

The hexagonal CdO nano-particles (CdO-NPs) was prepared using new nano Cd coordination polymer, [Cd(NO3)(bipy)(pzca)]n (1) as a precursor, through direct calcination process at 500 °C. The precursor (1) was synthesized by sonochemical method. The new nano compound (1) was characterized by IR spectroscopy, elemental analyses, X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and thermal gravimetric analyses. The structure of nano coordination polymer was determined by comparing the XRD pattern of nano and single-crystal of compound (1). The nano CdO was characterized by scanning electron microscopy (SEM) and X-ray powder diffraction (XRD). In addition, the activity and efficiency of nano CdO as an anti-cancer drug was studied on cancer cells with different concentration. The results shows that the viability of cancer cells reduced above 2 μg/mL of CdO-NPs concentration.

The Role of Weak Intermolecular Interactions in the Assembly of a Series of d10 Metal Coordination Polymers Based on N,Nʹ-Bis-Pyridin-3-Ylmethylene-Naphtalene-1,5-Diamine Ligand; Ultrasonic Synthesis, Spectroscopic and Structural Characterization

The motivation of this work is to highlight factors that influence the supramolecular structures of d10 metal coordination polymers. Two novel Hg(II) and Cd(II) 1D coordination polymers (CPs) have been constructed from metal iodide and a N,N′-bis-pyridin-3-ylmethylene-naphtalene-1,5-diamine ligand using conventional methods. Our analyses reveal the substantial role of weak hydrogen bonds and π–π stacking interactions in the assembly of these series of compounds. These compounds were studied using X-ray crystallography, infrared spectroscopy and X-ray powder diffraction. The supramolecular structures of these two compounds were compared with two structures that have been published recently. These coordination polymers in nano-size were synthesized under ultrasonication and their morphology were characterized using scanning electron microscopy (SEM).

The effect of different substituent groups of auxiliary ligands on the photochromic behaviors of bipyridinium-based coordination polymers

Two bipyridinium-based coordination polymers, {[Cd(BCbpy)2(o-BDC)]·13H2O} (1) and {[Cd(BCbpy)2(SA)]·6H2O} (2), have been synthesized and structurally characterized. Single-crystal X-ray diffraction analysis shows that the two compounds have similar one-dimensional coordination polymeric chain structures but different packing patterns. Compound 1 displays fast eye-detectable photochromic behavior while compound 2 is photoinert under 365nm irradiation. The influence of different substituent groups in same site of auxiliary ligands on the photochromic behaviors of the two compounds has been studied in detail.

Crystal structure of a compact three-dimensional metal-organic framework based on Cs+ and (4,5-di-cyano-1,2-phenyl-ene)bis-(phospho-nic acid).

A new metal-organic framework compound, poly[[μ7-dihydrogen (4,5-di-cyano-1,2-phenyl-ene)diphospho-nato]-(oxonium)caesium], [Cs(C8H4N2O6P2)(H3O)] n (I), based on Cs+ and the organic linker 4,5-di-cyano-1,2-phenyl-ene)bis-(phospho-nic acid, (H4cpp), containing two distinct coordinating functional groups, has been prepared by a simple diffusion method and its crystal structure is reported. The coordination polymeric structure is based on a CsO8N2 complex unit comprising a monodentate hydro-nium cation, seven O-atom donors from two phospho-nium groups of the (H2cpp)2- ligand, and two N-atom donors from bridging cyano groups. The high level of connectivity from both the metal cation and the organic linker allow the formation of a compact and dense three-dimensional network without any crystallization solvent. Topologically (I) is a seven-connected uninodal network with an overall Schäfli symbol of {417.64}. Metal cations form an undulating inorganic layer, which is linked by strong and highly directional O-H⋯O hydrogen-bonding inter-actions. These metallic layers are, in turn, connected by the organic ligands along the [010] direction to form the overall three-dimensional framework structure.

A novel one-dimensional double-chain-like ZnII coordination polymer: poly[bis(1-benzyl-1H-imidazole-κN3)tris(μ-cyanido-κ2C:N)(cyanido-κC)disilver(I)zinc(II)

One of most interesting systems of coordination polymers constructed from the first-row transition metals is the porous ZnII coordination polymer system, but the numbers of such polymers containing N-donor linkers are still limited. The title double-chain-like ZnII coordination polymer, [Ag2Zn(CN)4(C10H10N2)2]n, presents a one-dimensional linear coordination polymer structure in which ZnII ions are linked by bridging anionic dicyanidoargentate(I) units along the crystallographic b axis and each ZnII ion is additionally coordinated by a terminal dicyanidoargentate(I) unit and two terminal 1-benzyl-1H-imidazole (BZI) ligands, giving a five-coordinated ZnII ion. Interestingly, there are strong intermolecular AgI...AgI interactions between terminal and bridging dicyanidoargentate(I) units and C-H...π interactions between the phenyl rings of BZI ligands of adjacent one-dimensional linear chains, providing a one-dimensional linear double-chain-like structure. The supramolecular three-dimensional framework is stabilized by C-H...π interactions between the phenyl rings of BZI ligands and by AgI...AgI interactions between adjacent double chains. The photoluminescence properties have been studied.

Synthesis, structure and photoluminescence properties of lanthanoid coordination polymers based on tetra(3,5-dicarboxyphenoxymethyl)methane

A series of isostructural lanthanoid coordination polymers with the formula [Ln2(H6L)(H4L)(H2O)2]n (XL-Ln; Ln=SmIII, EuIII, GdIII, TbIII, DyIII; H8L=tetra(3,5-dicarboxyphenoxymethyl)methane) has been synthesized. The compounds (except XL-Gd) exhibit the characteristic emission of trivalent lanthanoid ions under UV irradiation. By using a mixture of EuIII/TbIII salts as starting material, color-tunable coordination polymers have been obtained of which the emission color can be changed from red to green with different EuIII/TbIII ratios.

CuII and ZnII β-diketonate coordination polymers based on pyrimidin-2-amine, pyrazine and 1,2-bis(4-pyridyl)ethane.

Copper(II) and zinc(II) bis(4,4,4-trifluoro-1-phenylbutane-1,3-dionato) compounds with pyrimidin-2-amine (pyr2a), pyrazine (pyz) and 1,2-bis(4-pyridyl)ethane (dpet) were prepared and solid-state structures of coordination polymers [M(tfpb)2(pyr2a)]∞ [M = Cu (1), Zn (2); tfpb = 4,4,4-trifluoro-1-phenylbutane-1,3-dionate], [M(tfpb)2(pyz)]∞ [M = Cu (3), Zn (4a, 4b)] and [Cu(tfpb)2(dpet)]∞ (5), respectively, were determined by single-crystal X-ray analysis. The coordination of metal centers in all compounds is octahedral with nitrogen ligands occupying the axial positions. Compound (1) crystallizes in the triclinic space group P\bar 1, whereas (2) crystallizes in the monoclinic space group P2/n. Differences are due to the different orientation of adjacent M(tfpb)2 units, whereas the orientation of pyrimidin-2-amine is the same in both compounds. Polymeric chains in (1) and (2) contain intramolecular N-H...O hydrogen bonding between amino and carbonyl groups. Room-temperature structures (3) and (4a) are isomorphous adopting the monoclinic space group C2/m; however, on cooling crystals (4a) to 150 K a single-crystal-to-single-crystal transformation to (4b) possessing the triclinic space group P\bar 1 was observed. Compound (5) crystallizes in the triclinic space group P\bar 1 and contains a parallel aggregation of chains in contrast to the known structure of the non-fluorinated benzoylacetonato ligand, where chains aggregate in a perpendicular fashion. In the compounds studied intramolecular C-H...O and/or C-H...F interactions are present. The neighboring chains are linked by π...π interactions and in some compounds also by C-H...π interactions [(1), (4b), (5)].

Synthesis, Crystal Structure and Thermal Stability of 1D Linear Silver(I) Coordination Polymers with 1,1,2,2-Tetra(pyrazol-1-yl)ethane

Two new linear silver(I) nitrate coordination polymers with bitopic ligand 1,1,2,2-tetra(pyrazol-1-yl)ethane were synthesized. Synthesized compounds were characterized by IR spectroscopy, elemental analysis, powder X-ray diffraction and thermal analysis. Silver coordination polymers demonstrated a yellow emission near 500 nm upon excitation at 360 nm. Crystal structures of coordination polymers were determined and structural peculiarities are discussed. In both of the structures, silver ions are connected via bridging ligand molecules to form polymeric chains with a five-atomic environment. The coordination environment of the central atom corresponds to a distorted trigonal bipyramid with two N atoms of different ligands in apical positions. The Ag–N bond distances vary in a wide range of 2.31–2.62 Å, giving strongly distorted metallacycles. Thermolysis of coordination polymers in reductive atmosphere (H2/He) leads to the formation of silver nanoparticles with a narrow size distribution.

Design and construction of diverse structures of coordination polymers: Photocatalytic properties

The reaction of Cu(NO3)2·3H2O/Ni(NO3)2·6H2O with 4′-(4-(3,5-dicarboxylphenoxy)phenyl)-4,2′:6′,4′′-terpyridine (H2dbp) gave [Cu0.5(Hdbp)]n (1) and [Ni(dbp)(H2O)]n (2), while the reactions of Co(NO3)2·6H2O with H2dbp in the presence of 4,4′-bipy and 2,2′-bpy generated [Co(dbp)(4,4′-bipy)]n (3) and {[Co(dbp)(2,2′-bipy)]n·H2O} (4), respectively (4,4′-bipy=4.4′-pyridine and 2,2′-bipy=2,2′-bipyridine). X-Ray single-crystal analyses reveal that 1 contains a 1D double chain. 2 possesses a 3D architecture with (4.620.83)2 topology that is interpenetrated with each other to form a 2-fold network. In 3, the 2D [Co(dbp)]n sheets are pillared by 4,4′-bpy to form a 3D framework with 1D open channel. Compound 4 consists of a 1D ladder-like chain. The results showed that the structural diversity of the coordination polymers resulted from the different geometries of metal ions and effect of assistant ligands. Furthermore, the photocatalytic properties of 1–4 for degradation of the methyl violet (MV) have been examined.

Structure and third-order nonlinear optical properties of the two-dimensional CoII coordination polymer [Co(1,2-BIB)(PA)]n {1,2-BIB is 1,2-bis[(1H-imidazol-1-yl)methyl]benzene and H2PA is phthalic acid}.

The design of nonlinear optical (NLO) materials with large NLO responses has been a challenge for materials scientists and chemists. Recently, organic polymers have received attention regarding their NLO properties and fast nonlinear response, and clusters involving delocalized dπ-pπ systems and conjugated dπ-pπ systems are expected to be a new class of NLO materials. Metal-organic coordination polymers combine the advantages of the organic and inorganic species. Thus far, tuning the third-order NLO properties of these materials has been a significant challenge. A two-dimensional coordination polymer, namely poly[(μ-benzene-1,2-dicarboxylato-κ3O1,O1':O3){μ-1,2-bis[(1H-imidazol-1-yl)methyl]benzene-κ2N3:N3'}cobalt(II)], [Co(C8H4O4)(C14H14N4)]n, was synthesized by hydrothermal methods. In the structure, the CoII ion is pentacoordinated by two N atoms from two different 1,2-bis[(1H-imidazol-1-yl)methyl]benzene (1,2-BIB) ligands and three O atoms from two symmetry-related benzene-1,2-dicarboxylate (isophthalate, PA) anions. The pentacoordinated CoII ions are linked by PA ligands to form a chain structure parallel to the c axis. Adjacent chains are further connected by 1,2-BIB ligands to produce a two-dimensional layered structure. The compound exhibits strong third-order nonlinear absorption and nonlinear refraction effects as a thin film. The third-order susceptibility χ(3) is calculated to be 1.07 × 10-8 esu, which is much larger than the values found for pure inorganic semiconductors and some polymers.