Copper Coordination Polymers Research Articles

1-D copper(I) coordination polymer based on bidentate 1,3-dithioether ligand: Novel catalyst for azide-alkyne-cycloaddition (AAC) reaction

A novel 1,3-bis(4-fluorophenylthio)-propane ligand based CuI 1-D polymeric coordination complex having formula ([(CuI)2{ArS(CH2)3SAr}2]n, Ar = 4-F-C6H4) has been synthesized and characterized by 1H NMR, 13C NMR and single crystal XRD techniques. This complex has been employed for the first time as suitable catalyst for base-free one-pot three-component regioselective azide-alkyne cycloaddition (AAC) reaction. A novel 1,2,3-triazole compound with sulfur functionalized pendant arms has also been prepared using our catalytic system in a multicomponent manner via one-pot two-step reaction.

Synthesis, crystal structure and magneto-structural studies of 2D copper(II) coordination polymer containing l-alanine amino acid

A 2D coordination polymer of Cu(II) was synthesized by the reaction of CuCl2·2H2O with l-alanine and characterized by elemental analysis, spectroscopic methods and single crystal X-ray studies. X-ray analysis indicated that the compound is a 2D coordination polymer which the carboxylate group of amino acid ligands acts as bridging ligand between Cu(II) ions. The crystal structure of compound is stabilized by intermolecular hydrogen bond interactions. Magnetic susceptibility data of powdered sample between 2 and 300 K were interpreted in terms of a 2D-spin model, with weak antiferromagnetic exchange-coupling through syn-anti carboxylate bridges, with coupling constant J = −0.2 cm−1 between nearest-neighbor Cu(II) ions. The results are compared with those obtained from similar studies in other copper amino acid complexes. DFT studies showed that overlap of magnetic dx2−y2 orbitals of the neighboring Cu(II) ions and the molecular orbitals of bridging carboxylate groups is negligible what makes only weak antiferromagnetic interaction between them. Thermal gravimetric analysis (TGA) indicated that the compound is stable up to 240 °C and it converts to CuO at about 800 °C. Cyclic voltammetry studies showed a quasi-reversible redox and an irreversible peaks which can be attributed to Cu(I)/Cu(II) and Cu(II)/Cu(III) couples, respectively.

Syntheses, structures and photocatalytic degradation of organic dyes for two isostructural copper coordination polymers involving in situ hydroxylation reaction

Two copper(II) coordination polymers, {[Cu2(btre)(hsuc)Cl(H2O)]·1.5H2O}n (1) and {[Cu2(btre)(hsuc)Br(H2O)]·1.5H2O}n (2) (btre = 1,2-bis(1,2,4-triazol-4-yl)ethane, H3hsuc = 2-hydroxysuccinic acid), were synthesized by the hydrothermal method via in situ hydroxylation reaction with fumarate (fum), btre and CuCl2/CuBr2, and characterized by elemental analyses, IR, TG and X-ray diffraction. 1 and 2 are isostructural and show a 4-connected 2-D network based on [Cu2O] dimers. 1 and 2 show good photocatalytic activity for the degradation of organic dyes methylene blue and methyl orange under UV light irradiation.

An unusual (4,6)-coordinated copper(II) coordination polymer: High efficient degradation of organic dyes under visible light irradiation and electrochemical properties

A copper(II) coordination polymer {[Cu(itp)(ip)][Cu4(OH)2(itp)(ip)3]·4H2O}n (1) (itp = 1-imidazol-1-yl-3-(1,2,4-triazol-4-yl)propane, ip = isophthalate) was synthesized and characterized. 1 exhibits an intriguing 2-fold interpenetrating array of (4,6)-coordinated 3D nets of the fsc topological type, which are based on the 4-coordinated single copper(II) and 6-coordinated tetranuclear hydroxy copper(II) [Cu4(μ3-OH)2] cluster. 1 is a highly efficient and universal photocatalyst for the degradation of the organic dyes methylene blue (MB), rhodamine B (RhB) and methyl orange (MO) under visible light irradiation. Electrochemical performance of 1 was also measured.

Synthesis and characterization of an inorganic-organic hybrid copper coordination polymer based on well-defined Keggin polyanions

Abstract A new inorganic-organic hybrid complex based on well-defined Keggin-type polyoxometalates and copper-lutidine assemblies, namely, [Cu3(3,5-Lutidine)6(PW12O40)]n (1), has been obtained under hydrothermal conditions and characterized by elemental analysis and single crystal X-ray diffraction. The X-ray diffraction analysis reveals that compound 1 is three-dimensional (3D) supramolecular structure with ‘sql’ topological 2D layer. The photocatalytic experiments indicate that 1 exhibit good catalytic activity for photodegradation of Rhodamine B (RhB) with UV irradiation. The thermal stabilities and fluorescent properties of this complex have also been studied.

Front Cover: Crystal Structure and Characterization of Two Layered Copper(II) Coordination Polymers with Anions of 3‐Phosphonopropionic Acid and (RS)‐2‐Phosphonobutyric Acid (Z. Anorg. Allg. Chem. 4/2018)

Front Cover: Crystal Structure and Characterization of Two Layered Copper(II) Coordination Polymers with Anions of 3‐Phosphonopropionic Acid and (<i>RS</i>)‐2‐Phosphonobutyric Acid (Z. Anorg. Allg. Chem. 4/2018)

Synthesis, crystal structures and magnetic properties of picolinate-bridged copper(II) chains

The paper reports the synthesis, crystal structures, and magnetic properties of two copper(II) coordination polymers, Cu2(L1)4 (1) and Cu3(L2)6 (2), based on rigid ethynylene-bridged ditopic ligands containing one picolinate subunit (L1 = 5-(pyridin-3-ylethynyl)picolinate anion; L2 = 5-((4-(methoxycarbonyl)phenyl)ethynyl)picolinate anion). Both 1 and 2 have a chain structure. In 1, the repeating unit in the chain is a doubly bridged picolinate dicopper(II) complex, whereas 2 is built upon trimeric units where the Cu2+ ions are also connected by double picolinate bridges. Both compounds exhibit antiferromagnetic interactions in the solid state. The magnetic properties of 1 and 2 were analyzed in terms of simple dimer (H = –2JSCuSCu) and linear trimer [H = –2J(SCu1SCu2+SCu2SCu1)] models, respectively, neglecting the intermolecular interactions between the polynuclear units. The values of the exchange coupling parameters were J = −0.59 and J = –0.30 cm−1 for 1 and 2, respectively.

Ph-Directed Assembly of Two 2D Copper(II) Coordination Polymers Based on Mixed Benzenetetracarboxylate and 1,4-bis(1,2,4-triazole-1-ylmethyl)-2,3,5,6-Tetrafluorobenzene Ligands: Syntheses, Structures and Properties

Two new Cu(II) coordination polymers [Cu(Fbtx)(H2btec)(H2O)2]n and {[Cu(Fbtx)(btec)0.5(H2O)2]·H2O}n have been synthesised by hydrothermal reactions of Cu(II) nitrate with 1,4-bis(1,2,4-triazole-1-ylmethyl)-2,3,5,6-tetrafluorobenzene (Fbtx) and 1,2,4,5-benzenetetracarboxylic acid (H4btec) under different pH conditions. The first complex has a two-dimensional four-connected layer structure with a 44-sql topology, whereas the second has a two-dimensional three-connected brick-wall network. The luminescence properties of the complexes in the solid state and their thermal stabilities have also been studied.

Crystal Structure and Characterization of Two Layered Copper(II) Coordination Polymers with Anions of 3‐Phosphonopropionic Acid and (RS)‐2‐Phosphonobutyric Acid

Blue single crystals of Cu[μ3‐O3P(CH2)2COOH]·2H2O (1) and Cu[(RS)‐μ3‐O3PCH(C2H5)COOH]·3H2O (2) were prepared in aqueous solutions (pH = 2.5–3.5). 1 crystallizes in space group Pbca (no. 61) with a = 812.5(2), b = 919.00(9), and c = 2102.3(2) pm. Cu2+ is fivefold coordinated by three oxygen atoms stemming from [O3P(CH2)2COOH]2– anions and two water molecules. The Cu–O bond lengths range from 194.0(3) to 231.8(4) pm. The connection between the [O3P(CH2)2COOH]2– anions and the Cu2+ cations yields a polymeric structure with layers parallel to (001). The layers are linked by hydrogen bonds. 2 crystallizes in space group Pbca (no. 61) with a = 1007.17(14), b = 961.2(3), c = 2180.9(4) pm. The copper cations are surrounded by five oxygen atoms in a square pyramidal fashion with Cu–O bonds between 193.6(4) and 236.9(4) pm. The coordination between [O3PCH(C2H5)COOH]2– and Cu2+ results in infinite puckered layers parallel to (001). The layers are not connected by any hydrogen bonds. Each layer contains both R and S isomers of the [O3PCH(C2H5)COOH]2– dianion. Water molecules not bound to Cu2+ are intercalated between the layers. UV/Vis spectra suggest three d–d transition bands at 743, 892, 1016 nm for 1 and four bands at 741, 838, 957, and 1151 nm for 2, respectively. Magnetic measurements suggest a weak antiferromagnetic coupling between Cu2+ due to a super‐superexchange interaction. Thermoanalytical investigations in air show that the compounds are stable up to 95 °C (1) and 65 °C (2), respectively.

A Semiconducting Copper(II) Coordination Polymer with (4,4) Square Grid Topology: Synthesis, Characterization, and Application in the Formation of a Photoswitch

A phenoxo and end-to-end thiocyanate bridged copper(II) coordination polymer (CP), [Cu2L2(μ-1,3-SCN)2]n, where HL is an potential tetradentate N2O2 donor Schiff base ligand, 2-(2-(ethylamino)ethylimino)methyl)-6-ethoxyphenol, has been synthesized and characterized. The band gap, bulk capacitance, electron lifetime, relaxation time, dielectric constant, and DC conductivity of the complex in the solid state have been studied. Variable temperature magnetic susceptibility measurement indicates the presence of weak antiferromagnetic interactions among the copper(II) centers with J = −0.97 cm–1. The complex shows increase in conductivity when illuminated with visible light (photosensitivity ∼2.833).

Synthesis and Investigations of Chiral NNO Type Copper(II) Coordination Polymers

AbstractHerein, we report the synthesis and characterizations of chiral copper(II) coordination polymers (CPs) based on Schiff base of (S)‐2‐aminomethylpyrrolidine and salicylaldehyde derivatives. Single crystal X‐ray analysis showed that copper(II) complex is 1D CP, with the repeating units LCu‐OAc (L=ligand) organized in a perpendicular manner, where the copper(II) atoms are six‐coordinated and have a distorted octahedral geometry. Also complex with chlorine counter ion having unusual dimeric structure was synthesized and characterized. It was demonstrated that CPs catalyze the enantioselective Henry reaction with up to 78% ee.

Magnetostructural relationships in polymorphic ethylmalonate-containing copper(ii) coordination polymers

Three ethylmalonate-containing non-centrosymmetric copper(ii) coordination polymers with magnetic properties ranging from antiferromagnetism to ferromagnetic ordering are synthetized under nearly identical conditions.

Coordination ability of amino acid hydrazide ligands and their influence on magnetic properties in copper(ii) coordination polymers

Copper(ii) coordination polymers constructed from newly synthesized amino acid hydrazides and 4,4′-bipyridine exhibit antiferromagnetic ordering mediated through hydrazide bridges.

PH-Induced fragmentation of colloids based on responsive self-assembled copper(ii) metallopolymers

Responsive colloids made from copper(ii) coordination polymers are readily dissolved in acidic medium following a controlled depolymerization of the polymer chains.

A novel 2D coordination network built from hexacopper(i)-iodide clusters and cagelike aminophosphine blocks for reversible “turn-on” sensing of aniline

An unique copper(i) coordination polymer was prepared, characterized and applied as a luminescence sensor for aniline recognition.

Chiral and achiral 1D copper(ii) coordination polymers based on glycolato and chelating aromatic diamine ligands

New chiral and achiral 1D coordination polymers based on glycolato and chelating aromatic diamine ligands.

Nonlinear optical and G-Quadruplex DNA stabilization properties of novel mixed ligand copper(II) complexes and coordination polymers: Synthesis, structural characterization and computational studies

The present study reports the synthesis and evaluation of nonlinear optical property and G-Quadruplex DNA Stabilization of five novel copper(II) mixed ligand complexes. They were synthesized from copper(II) salt, 2,5- and 2,3- pyridinedicarboxylic acid, diethylenetriamine and amide based ligand (AL). The crystal structure of these complexes were determined through X-ray diffraction and supported by ESI-MAS, NMR, UV–Vis and FT-IR spectroscopic methods. Their nonlinear optical property was studied using Gaussian09 computer program. For structural optimization and nonlinear optical property, density functional theory (DFT) based B3LYP method was used with LANL2DZ basis set for metal ion and 6-31G∗ for C,H,N,O and Cl atoms. The present work reveals that pre-polarized Complex-2 showed higher β value (29.59 × 10−30e.s.u) as compared to that of neutral complex-1 (β = 0.276 × 10−30e.s.u.) which may be due to greater advantage of polarizability. Complex-2 is expected to be a potential material for optoelectronic and photonic technologies. Docking studies using AutodockVina revealed that complex-2 has higher binding energy for both G-Quadruplex DNA (−8.7 kcal/mol) and duplex DNA (−10.1 kcal/mol). It was also observed that structure plays an important role in binding efficiency.

A Three-Dimensional Copper Coordination Polymer Constructed by 3-Methyl-1H-pyrazole-4-carboxylic Acid with Higher Capacitance for Supercapacitors

A three-dimensional (3D) copper-based coordination polymer, ([Cu(H2mpca)(tfbdc)], Cu-CP; H2mpca = 3-methyl-1H-pyrazole-4-carboxylic acid; H2tfbdc = 2,3,5,6-tetrafluoroterephthalic acid), has been synthesized and characterized by IR spectroscopy, thermogravimetric analysis, elemental analysis, and single-crystal X-ray diffraction. In Cu-CP, each Cu(II) ion is located in a triangular bipyramid geometry, and these Cu(II) ions are linked by tfbdc2– ligands to produce a 3D network. Variable-temperature magnetic susceptibility data display that weak antiferromagnetic interactions between the adjacent Cu (II) ions exist in Cu-CP. Cu-CP was evaluated as an electrode material for supercapacitors. It displayed a higher specific capacitance of 735 F g–1 in 1 M KOH solution at a current density of 1 A g–1 and remained at 375 F g–1 after 1500 cycles at 2 A g–1.

A new Cu(II) three-dimensional network with 4,4′-oxybis benzoic acid: structural diversity, EPR, and magnetism

The copper derivative {[Cu4(oba)4(H2O)4]∙H2O}n (1) has been hydro(solvo)thermally synthesized by combining flexible 4,4′-oxybis benzoic acid (oba) and divalent copper nitrate. As a result of the potential coordination modes of carboxylate oxygens from the oba ligand, the aforementioned complex leads to the formation of an interesting 3D framework, as evidenced by single-crystal X-ray diffractometry. Concerning the topology in 1, the dimers [Cu2C4O8] are nodes of a 5-fold 4-connected uninodal net of the type lvt, with point symbol {42.84} and vertex symbol [4.4.84.84.88.88]. The encapsulation of the copper coordination polymer displays a moderate luminescent property. On temperature-dependent magnetic study, it reveals that the magnetic behaviour of 1 can be associated to a strong antiferromagnetic coupling between the two Cu(II) ions.

Coordination Polymers Containing 1,3-Phenylenebis-((1H-1,2,4-triazol-1-yl)methanone) Ligand: Synthesis and ε-Caprolactone Polymerization Behavior.

The reaction of isophthaloyl dichloride with 1H-1,2,4-triazole afforded the new ligand 1,3-phenylenebis(1,2,4-triazole-1-yl)methanone (1). A series of Co(II), Cu(II), Zn(II) and Ni(II) complexes were synthesized using 1 and then characterized by melting point analysis, elemental analysis, theoretical calculations, thermogravimetric analysis, X-ray powder diffraction, nuclear magnetic resonance, infrared and Raman spectroscopy. Experimental and computational studies predict the formation of coordination polymers (CPs). The cobalt and copper CPs and zinc(II) complex were found to be good initiators for the ring-opening polymerization of ε-caprolactone (CL) under solvent-free conditions. 1H-NMR analysis showed that the obtained polymers of CL were mainly linear and had terminal hydroxymethylene groups. Differential scanning calorimetry showed that the obtained polycaprolactones had high crystallinity, and TGA showed that they had decomposition temperatures above 400 °C. These results provide insight and guidance for the design of metal complexes with potential applications in the polymerization of CL.