Copper Coordination Polymers Research Articles

Copper coordination polymers with selective hole conductivity

Low-dimensional copper coordination polymers represent an alternative, unprecedented class of charge transport materials, comprised of molecular building blocks.

Room temperature ferroelectric copper(ii) coordination polymers based on amino acid hydrazide ligands

This work brings into focus the superior coordination properties and facile applicability of amino acid hydrazide ligands for the design of molecular magnets and molecular ferroelectrics.

Synthesis, Characterization, Ion-Exchange, and Catalytic Properties of Three Isostructural Copper(Ii) Coordination Polymers with a Flexible Bis(Triazole) Ligand

Synthesis, Characterization, Ion-Exchange, and Catalytic Properties of Three Isostructural Copper(Ii) Coordination Polymers with a Flexible Bis(Triazole) Ligand

Influence of Functional Groups on Structures, Properties and Biological Activity of Three Novel Copper Coordination Polymer Based on Carboxylate Ligands and Imidazole

Influence of Functional Groups on Structures, Properties and Biological Activity of Three Novel Copper Coordination Polymer Based on Carboxylate Ligands and Imidazole

An Uneven Chain-like Ferromagnetic Copper(II) Coordination Polymer Displaying Metamagnetic Behavior and Long-Range Magnetic Ordering

Ferromagnetic coupling exists in an uneven chain-like copper(II) complex with both end-on azido and syn-syn carboxylato bridges, (Cu3(L)2(N3)4(H2O)3)n (1, HL = 6-hydroxynicotinic acid). It is the first example of one-dimensional (1D) chain-like copper(II) coordination polymer showing both metamagnetic behavior and long-range magnetic ordering (Tc = 6.7 K), thanks to the interchain hydrogen bonds, which make a three-dimensional (3D) supramolecular array of the entire molecular structure and mediate the interchain antiferromagnetic interaction.

Two-dimensional zinc(II) and copper(I) coordination polymers for photoluminescence

Two-dimensional (2-D) coordination polymers [Zn2(bpab)(CH3CO2)4]·H2O (1), [Zn(bpab)(H2O)2](NO3)2 (2), [Cu2(bpab)I2]·CH3OH (3), and [Cu2(tpmd)I2] (4) have been synthesized by the reaction of zinc(II)/copper(I) ions and tetradentate polypyridine ligands (bpab = bis-1,4-(di-4-pyridylaminomethyl)benzene and tpmd = N,N,N',N'-tetrakis(pyridine-4-yl)methanediamine). The zinc(II) ions of 1 and 2 have distorted tetrahedral and trigonal bipyramidal geometries, respectively. By coordinating zinc(II) ions and bpab ligands, 1 and 2 formed a brick wall and puckered 2-D networks, respectively. The copper(I) ions of 3 and 4 are both tetrahedral structures with Cu2I2 rhomboidal geometry. By linking the Cu2I2 cores and bpab/tpmd ligands, 3 and 4 exhibited interwoven and interconnected bilayered 2-D networks, respectively. Compared to free bpab and tpmd ligands, polymers 1 and 2 show strongly blue-shifted emissions, whereas polymers 3 and 4 show strongly red-shifted emissions. Therefore, the shifts of emission wavelengths are strongly dependent on the zinc(II) and copper(I) ions that linked the bpab/tpmd tetradentate ligands, respectively.

Coordination polymer of a tetranuclear copper(II) complex: structural characterization, computational investigation and spectral study

Coordination polymer of a tetranuclear copper(II) complex: structural characterization, computational investigation and spectral study

Topology of two copper(II) coordination polymers with tetra(triazole) and dicarboxylate, photocatalytic and sonocatalytic decomposition of MB

Two Cu(II) coordination polymers, {[Cu(ttpe)0.5(1,3-bdc)]·2H2O·DMAC}n (1) and {[Cu(ttpe)0.5(1,3-bda)]·3H2O}n (2) (ttpe = 1,1,2,2-tetrakis(1,2,4-triazol-1-yl)phenyl)ethylene, 1,3-bdc = 1,3-benezenedicarboxylate, 1,3-bda = 1,3-benzenediacetate), were hydrothermally prepared and characterized. 1 exhibited (4,4)-coordinated 2-D topology with point symbol (3 2 ·6 2 ·7 2 )(3 2 ·6 2 ·7 2 )2. 2 showed (3,4)-coordinated 2-D topology with point symbol (4·6·8)2(4 2 ·6 2 ·8 2 ). E g data of 1 and 2 were 2.31 and 2.17 eV. 1 and 2 exhibited good catalytic activity for degradation of MB under visible light and ultrasound. The degradation mechanisms using 1 and 2 were explored.

RETRACTED ARTICLE: A new one-dimensional copper(II) coordination polymer: crystal structure and treatment activity on diabetic nephropathy

We, the Editors and Publisher of the journal Inorganic and Nano-Metal Chemistry, have retracted the following article: Pan-Pan Lin, Qiao-Ling Xie & Ling-Wei Chen. A new one-dimensional copper (II) coordination polymer: crystal structure and treatment activity on diabetic nephropathy, Inorganic and Nano-Metal Chemistry. 2021; AHEAD-OF-PRINT, 1-5. DOI: 10.1080/24701556.2021.1988974 Since publication, concerns have been raised about the integrity of the data in the article. When approached for an explanation, the authors have been unable to address the concerns raised and have not been able to provide sufficient supporting information. As verifying the validity of published work is core to the integrity of the scholarly record, we are therefore retracting the article. The corresponding author listed in this publication has been informed. The authors have agreed to retract the article. We have been informed in our decision-making by our policy on publishing ethics and integrity and the COPE guidelines on retractions. The retracted article will remain online to maintain the scholarly record, but it will be digitally watermarked on each page as ‘Retracted’.

Comprehensive and High-throughput Electrolysis of Water and Urea by 3-5 nm Nickel and Copper Coordination Polymers.

Metal-organic coordination polymers (CP) have attracted the scientific attention for electrochemical water oxidation as it has the similar coordination structure like natural photosynthetic coordinated complex. However, the harsh synthesis conditions and bulky nature pose a major challenge in the field of catalysis. Herein, 3-5 nm CP particles synthesized at room temperature using aqueous solutions of Ni2+ /Cu2+ and 2,5-dihydroxyterepthalic acid as precursor were applied for alkaline water and urea electrolysis. The overpotential required is only 300 mV at 10 mA cm-2 by Nano-Ni CP for water oxidation, with turnover frequency (TOF) of 21.4 s-1 which is around 8 times higher than its bulk-counterpart. Overall water and urea splitting were achieved with Nano-Cu (-) ∥ Nano-Ni (+) couple on Ni foam at 1.69 and 1.52 V to achieve 10 mA cm-2 , respectively. High electrochemical surface area (ECSA), high TOF, and enhanced mass diffusion are found to be the key parameters responsible for the state-of-the-art water and urea splitting performances of nano-CPs as compared to their bulk counterparts.

Organic Light-Emitting Diodes Based on Luminescent Self-Assembled Materials of Copper(I)

Over the past decade, we have seen the rapid advancement in the technology of organic light-emitting diodes (OLEDs) toward practical applications. The high color contrast, wide viewing angles, good flexibility, and low power consumption of OLEDs have rendered them promising candidates for next-generation displays and solid-state lighting applications. Parallel to the optimization in device structures, of equal importance is the search for new classes of emitters. While conventional OLEDs mainly rely on triplet emitters based on precious metal complexes, such as those of platinum(II) and iridium(III), copper(I) self-assembled materials represent attractive alternatives with relatively low cost but comparable emission tunability. In this mini review, the recent progress in the development of copper(I) self-assembled materials, including copper(I) clusters and coordination polymers, as electroluminescent materials in OLEDs will be discussed.

Synthesis and characterization of Manganese(II), Cobalt(II) and Copper(II) coordination polymers with a flexible zwitterionic based ligand

Four new coordination polymers, formulated as {[MnCl(µ-bipna)](NO3)⋅2H2O}n (1), {[CoCl2(µ-bipna)]⋅2H2O}n (2), {[CuCl(µ4-bipna)]BF4⋅2H2O}n (3) and {[CuCl(µ4-bipna)]ClO4⋅2H2O}n (4) where H2bipnaBr2 = 1,1′-(1,1′-biphenyl-4,4′-diylbis(methylene))bis(3-carboxypyridin-1-ium) bromide, were synthesized under solvothermal conditions. Their structures have been characterized by single crystal and powder X-ray diffraction analyses, infrared spectra (IR) and elemental analyses. Complexes 1, 3 and 4 are isostructural and display 3-fold interpenetrated 2D → 2D structures with sql topology and the point symbol 44.62. Complex 2 exhibits a 1D coordination polymer structure, which becomes a stacked 3D supramolecular structure by hydrogen bonding and π⋅⋅⋅π interactions. The structural diversity of the compounds could be due to the conformation of the flexible zwitterionic ligands. In 2, the bipna ligand displays a cis-conformation, while in the other compounds the ligand shows a trans-conformation. The thermal and optical properties of the compounds were investigated.

Crystal structure, Hirshfeld surface analysis and physicochemical studies of a new copper coordination polymer with 3,3’-diaminodiphenylsulfone as ligand

A new copper coordination polymer [Cu(DDS)Cl2H2O]n(3,3’-diaminodiphenylsulfone denoted DDS) was synthesized by the slow evaporation method of aqueous solution at room temperature. The obtained complex was characterized by single crystal X-ray diffraction, spectroscopic measurements (IR, Raman and UV-visible absorption) and thermal analysis (TGA and DSC). The examination of the molecular structure shows that the crystal packing can be described as organic-inorganic mixed layers parallel to (a, b) plane. These layers are built of parallel helix linked to each others by hydrogen bonds. In each helix the copper central metal is bound to two ligands and the ligand bridges two coppers. The cohesion among layers, within each helix and between the adjacent helix is assured by N-H…Cl, N-H…O, C-H…O, C-H…Cl, O-H…O and O-H…Cl hydrogen bonding interactions forming a three dimensional network. Hirshfeld Surface analysis (HS) highlights that H...H, H…Cl/Cl…H and O…H/H…O are the most important interactions. Also, functional fragments present in the synthesized copper complex were identified by infrared and Raman studies. In addition, the optical properties were also investigated by UV-vis absorption showing four bands at 291, 365, 448 and 715 nm. Furthermore, TGA and DSC analysis prove that the synthesized compound is stable up to 130°C.

Crystal structure and magnetic interactions of a new alkoxido and azido bridged 1D copper(II) coordination polymer

A new 1D azido and alkoxido-bridged Cu(II) coordination polymer, [Cu2(H3L)(μ-H2L)(μ-N3)]n (1), was synthesized from the reaction of H4L, Cu(NO3)2·3H2O and NaN3 in methanol, where H4L is (E)-2-((5-bromo-2-hydroxybenzylidene)amino)-2-(hydroxymethyl)propane-1,3-diol. Compound 1 was characterized by elemental analysis, spectroscopic methods and single-crystal X-ray diffraction. Both spectroscopic and structural studies confirmed the presence of the Schiff base and the azide ligands. Azido and alkoxido bridges connect two Cu(II) ions with different coordination environments. The Schiff base ligand, H4L, shows two coordination modes acting as H3L− and H2L2− to the metal cores. The azido ligands show both end-on and end-to-end bridging modes. The magnetic study performed in the 1.8–300 ​K range shows an overall ferromagnetic interaction among the copper(II) ions dominated by the coupling through the alkoxido bridge. We have calculated the value of the magnetic coupling constants by means of DFT calculations, and we compared their values with those obtained from the magnetic susceptibility measurements.

An ultrathin amino-acid based copper(II) coordination polymer nanosheet for efficient epoxidation of β-caryophyllene

• CuIle-e nanosheet and CuIle-m nanoshuttle were fabricated from natural amino acid. • Stable catalytic systems, CuIle-e /acetone/TBHP and CuIle-e /THF/O 2 /TBHP, were built. • Good yields (86.1% or 87.2%) for β-caryophyllene epoxide were achieved. • Superior recyclability of CuIle-e nanosheet was realized. Natural amino acids are important building blocks for the construction of intriguing coordination polymers (CPs) because of their abundance, inexpensiveness and environmental benignness. Herein, two copper(II) CPs, namely, 2D CuIle-e nanosheet ( e : ethanol) and 1D CuIle-m nanoshuttle ( m : methanol), were fabricated from L -isoleucine ( Ile ) and well characterized with single-crystal x-ray diffraction, XPS spectra, TEM and AFM, etc. More importantly, two novel and stable catalytic nanosystems, i.e. CuIle-e /acetone/TBHP ( tert-butyl hydroperoxide) and CuIle-e /THF/O 2 /TBHP, were thus conveniently built by using ultrathin 2D CuIle-e nanosheet (~ 2.3 nm) in suitable aprotic solvents. Under mild conditions, complete conversion of β-caryophyllene and good yields (86.1% or 87.2%) for β-caryophyllene epoxide were gained via CuIle-e /acetone/TBHP or CuIle-e /THF/O 2 (1 atm)/TBHP (10.0 mol%), respectively. Notably, ultrathin CuIle-e nanosheet showed fairly satisfactory stability, which may open a unique window for the facile fabrication of new amino-acid based CP nanosystems with outstanding catalytic performances in actual applications. Two amino acid-based ultrathin CP nanosystems, CuIle-e /acetone/TBHP and CuIle-e /THF/1 atm O 2 /TBHP, were employed for the highly efficient epoxidation of β-caryophyllene under mild conditions.

Synthesis, characterization and fluorescence properties of mixed-ligand cobalt(II), copper(II), zinc(II) and cadmium(II) coordination polymer complexes involving 4,4’-bipyridine and 2,5-pyridinedicarboxylic acid

Four mixed-ligand coordination polymer complexes of cobalt(II), copper(II), zinc(II), and cadmium(II) were synthesized by solvothermal method in 1:1:1 metal: 4,4’-bipy: 2,5-pdc molar ratio using 2,5-pyridinedicarboxylic acid (2,5-pdc) and 4,4’-bipyridine (4,4’-bipy). These complexes are viz; 1. [Co2(4,4'-bipy)(2,5-pdc)2(H2O)4]n 2. [Cu2(4,4'-bipy) (2,5-pdc)2]n 3. [Zn2(4,4'-bipy)(2,5-pdc)2(H2O)4]n and 4. [Cd3(4,4'-bipy)(2,5-pdc)2(OOCCH3)2(H2O)4]n.. All these complexes (1-4) have been characterized by elemental analyses (C,H,N), FT-IR-spectra, thermal analyses (TGA/DTA/DTG), fluorescence spectra and powder X-ray diffraction (PXRD) analyses to arrive at conclusion regarding their geometrical structure.

Synthesis, characterization, optical and electrochemical performances of 3-fold interpenetrated Copper(II) coordination polymer with a flexible zwitterionic ligand

A new Cu(II)-coordination polymer, formulated as {[CuCl(μ4-bipna)](NO3)·2.5H2O}n (1) ((H2bipna)Br2: 1,1'-([1,1′-biphenyl]-4,4′-diylbis (methylene))bis (3-carboxypyridin-1-ium) bromide) was synthesized and characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction technique. The single crystal X-ray diffraction analysis revealed that compound 1 exhibited a 2D→2D polycatenane of 3-fold interpenetrated sql layers. The electrochemical performance of 1 was performed both as anode and cathode for Li-ion batteries. In both situations, the capacity values remained around 20–40 mAhg−1 independent of type of the electrodes. In addition, the thermal and optical properties of compound 1 were investigated.

Time-Dependent Self-Assembly of Copper(II) Coordination Polymers and Tetranuclear Rings: Catalysts for Oxidative Functionalization of Saturated Hydrocarbons.

This study describes a time-dependent self-assembly generation of new copper(II) coordination compounds from an aqueous-medium reaction mixture composed of copper(II) nitrate, H3bes biobuffer (N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid), ammonium hydroxide, and benzenecarboxylic acid, namely, 4-methoxybenzoic (Hfmba) or 4-chlorobenzoic (Hfcba) acid. Two products were isolated from each reaction, namely, 1D coordination polymers [Cu3(μ3-OH)2(μ-fmba)2(fmba)2(H2O)2]n (1) or [Cu2(μ-OH)2(μ-fcba)2]n (2) and discrete tetracopper(II) rings [Cu4(μ-Hbes)3(μ-H2bes)(μ-fmba)]·2H2O (3) or [Cu4(μ-Hbes)3(μ-H2bes)(μ-fcba)]·4H2O (4), respectively. These four compounds were obtained as microcrystalline air-stable solids and characterized by standard methods, including the single-crystal X-ray diffraction. The structures of 1 and 2 feature distinct types of metal-organic chains driven by the μ3- or μ-OH- ligands along with the μ-benzenecarboxylate linkers. The structures of 3 and 4 disclose the chairlike Cu4 rings assembled from four μ-bridging and chelating aminoalcoholate ligands along with μ-benzenecarboxylate moieties playing a core-stabilizing role. Catalytic activity of 1-4 was investigated in two model reactions, namely, (a) the mild oxidation of saturated hydrocarbons with hydrogen peroxide to form alcohols and ketones and (b) the mild carboxylation of alkanes with carbon monoxide, water, and peroxodisulfate to generate carboxylic acids. Cyclohexane and propane were used as model cyclic and gaseous alkanes, while the substrate scope also included cyclopentane, cycloheptane, and cyclooctane. Different reaction parameters were investigated, including an effect of the acid cocatalyst and various selectivity parameters. The obtained total product yields (up to 34% based on C3H8 or up to 47% based on C6H12) in the carboxylation of propane and cyclohexane are remarkable taking into account an inertness of these saturated hydrocarbons and low reaction temperatures (50-60 °C). Apart from notable catalytic activity, this study showcases a novel time-dependent synthetic strategy for the self-assembly of two different Cu(II) compounds from the same reaction mixture.

Two-Dimensional Copper Coordination Polymer Assembled with Fumarate and 5,5’-Dimethyl-2,2’-bipyridine: Synthesis, Crystal Structure and Magnetic Properties

[[Cu(fum)(dmb)]·H2O]n (1) (fum = fumarate; dmb = 5,5’-dimethyl-2,2’-bipyridine) was obtained by a self-assembly solution reaction, at ambient conditions, and characterized by elemental analysis, IR spectroscopy and X-ray single crystal diffraction. Crystallographic studies show that 1 crystallizes in a triclinic system with a P-1 space group, with a = 8.2308(2) A, b = 9.7563(2) A, c = 10.3990(2) A; α = 80.3444(4)°, β = 77.9517(4)°, γ = 82.0440(5)°; V = 800.45(3) A3. The Cu(II) centers are five-coordinated with a distorted square pyramidal configuration. The formation of a two-dimensional (2D) array in 1 can be explained by the presence of two different coordination modes in the fumarate ligand: μ-η1:η0 and μ2-η2:η0, both in a bridging monodentate manner, the latter generating distinctive rhombic-dinuclear units. The thermal stability of 1 has also been analyzed. Magnetic measurements revealed that this polymer exhibits weak antiferromagnetic ordering. [[Cu(fum)(dmb)]·H2O]n, exhibiting weak antiferromagnetic interactions, displays a two-dimensional array comprised of rhombic dinuclear units, where the carboxylate moieties of fumarate bridging ligand displays monodentate and oxo-bridging coordination modes connecting two Cu centers.

Cover Feature: Self‐Assembly and Aggregation‐Induced Emission in Aqueous Media of Responsive Luminescent Copper(I) Coordination Polymer Nanoparticles (Chem. Eur. J. 32/2021)

Cover Feature: Self‐Assembly and Aggregation‐Induced Emission in Aqueous Media of Responsive Luminescent Copper(I) Coordination Polymer Nanoparticles (Chem. Eur. J. 32/2021)