Two-dimensional Coordination Polymer Research Articles

A novel silver(I) two-dimensional coordination polymer of thiophosphoric triamide ligand with two different coordination modes: Experimental, theoretical and molecular docking study

A novel silver(I) two-dimensional coordination polymer of thiophosphoric triamide ligand with two different coordination modes: Experimental, theoretical and molecular docking study

Synthesis and structure of a non-van-der-Waals two-dimensional coordination polymer with superconductivity

Two-dimensional conjugated coordination polymers exhibit remarkable charge transport properties, with copper-based benzenehexathiol (Cu-BHT) being a rare superconductor. However, the atomic structure of Cu-BHT has remained unresolved, hindering a deeper understanding of the superconductivity in such materials. Here, we show the synthesis of single crystals of Cu3BHT with high crystallinity, revealing a quasi-two-dimensional kagome structure with non-van der Waals interlayer Cu-S covalent bonds. These crystals exhibit intrinsic metallic behavior, with conductivity reaching 103 S/cm at 300 K and 104 S/cm at 2 K. Notably, superconductivity in Cu3BHT crystals is observed at 0.25 K, attributed to enhanced electron-electron interactions and electron-phonon coupling in the non-van der Waals structure. The discovery of this clear correlation between atomic-level crystal structure and electrical properties provides a crucial foundation for advancing superconductor coordination polymers, with potential to revolutionize future quantum devices.

Fabrication of two novel two-dimensional copper-based coordination polymers regulated by the “V”-shaped second auxiliary ligands as high-efficiency urease inhibitors

Two novel copper-based coordination polymers (Cu-CPs) had been presented based on mixed ligands. The synthetic Cu-CP-1 and Cu-CP-2 were derived from a combination of two distinct forms of “V”-shaped bis-pyridine-bis-amide ligands and 1,2,4-benzenetricarboxylic acid (1,2,4-H3BTC). Distinct grid windows were seen in the simplified two-dimensional (2D) layers of the Cu-CPs due to the variable length of ligand regulation. These Cu-CPs had the potential to act as urease inhibitors (UIs), and the mechanisms responsible for their inhibition were extensively studied. The results indicated that both Cu-CPs exhibited significant urease inhibitory activities with urease inhibition rates of 88.02 % and 88.87 % at 100 µM and semi-inhibitory levels of IC50 of 0.92 ± 0.05 µM and 0.87 ± 0.03 µM, respectively. Furthermore, the inhibitory activities of the Cu-CPs were higher than those of the standard thiourea. An investigation of the enzyme kinetics of the Cu-CPs using Lineweaver–Burk (L–B) plots at various inhibitor doses demonstrated their non-competitive inhibitory nature, enhancing our comprehension of the possible mechanism by which these Cu-CPs exert urease inhibition. Furthermore, molecular docking was used to verify the interactions between Cu-CPs and the urease active site. The findings of the urease inhibition studies were good, and the impact of Cu-CP complexes on urease inhibition was examined using density functional theory (DFT) simulations.

Strategic Advancement in Inner Filter Effect Controllable Detection of Tetracyclines and Nitroaromatics in Real-World Matrices by Two-Dimensional Coordination Polymer

Strategic Advancement in Inner Filter Effect Controllable Detection of Tetracyclines and Nitroaromatics in Real-World Matrices by Two-Dimensional Coordination Polymer

Solvent-free CO2 cycloaddition by one- and two-dimensional sodium coordination polymers based on hydrazonic ligands

We successfully synthesized and characterized four new coordination polymers of sodium: sodium 4-hydroxy-3-{[2-(pyridine-4-carbonyl)hydrazinylidene]methyl}benzene-1-sulfonate (NaL4-Py), sodium 3-[(2-benzoylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (NaLPh), sodium 3-[(2-acetylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (NaLMe), and sodium 3-[(2-carbamoylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (NaLNH2). These polymers were synthesized through a 1:1 condensation reaction of hydrazide derivatives with sodium salicylaldehyde-5-sulfonate monohydrate (NaSalSO3) and were thoroughly characterized using various analytical techniques. The compounds NaLMe and NaLPh, crystallized in the P 1‾ and P21/n space groups, respectively, forming one-dimensional polymers. On the other hand, NaLNH2 and NaL4-Py crystallized in the Cmca and P 1‾ space groups, respectively, forming two-dimensional coordination polymers. The coordination environment of the sodium cation differed among the compounds, with the imine nitrogen atom interfering in NaL4-Py and NaLPh. The sulfonate group exhibited various coordination modes, resulting in the different dimensionalities of the polymers. Compounds NaL4-Py and NaLPh acted as heterogeneous Lewis acid catalysts for the solvent-free cycloaddition reaction of epichlorohydrine and CO2 into valued cyclic carbonate. High selective conversion (68 %) of epichlorohydrin to cyclic carbonate was obtained at mild conditions, 60 °C and 1 bar CO2, after 24 h of reaction.

A terbium coordination polymer based on mixed rigid and flexible organic ligands as a luminescent sensor for the convenient visual detection of ascorbic acid

Ascorbic acid (AA) is an essential antioxidant in the human body, whose detection is of significance in many fields. In this study, a two-dimensional terbium coordination polymer [Tb (dlba) (phen)]n (Tb-CP) based on a rigid 1,10-phenanthroline (phen) and a flexible 2-(3,5-dicarboxybenzyloxy) benzoic acid unit (H3dlba) was prepared under the hydrothermal conditions and characterized by Powder X-ray diffraction, elemental analysis, thermogravimetric analysis, infrared spectroscopy and single crystal X-ray diffraction. The Tb-CP synthesized via the mixed ligand strategy exhibits excellent water stability and acid-alkali resistance. As a luminescent sensor, the Tb-CP showed bright green luminescence characteristics of Tb3+, which was quenched after the addition of AA, with a quenching efficiency of 95.3 %. Additionally, the sensor shows high sensitivity and a rapid response time of 30 s. The detection limit is as low as 55.4 nM. In the actual sample test, the recovery rate of AA was 95–105 % (RSD< 1 %), indicating that the sensor has the potential for practical application. Furthermore, an integrated system based on Tb-CP and a smartphone can be employed for the visual detection of AA.

A two-dimensional copper coordination polymer and its g-C3N4 composite for efficient photocatalytic degradation of organic dyes

A two-dimensional copper coordination polymer {[Cu2(tmipa)2(tfpt)2]·8·5H2O·CH3CN}n (Cu(tmipa)) (tmipa = tris(4-(2-methyl-1H-imidazol-1-yl)phenyl)amine, H2tfpt = 3,4,5,6-tetrafluorophthalic acid) was synthesized by solvothermal method. It has a (3,3)-connected two-dimensional structure. A series of Cu(tmipa)/wt%g-C3N4 composites (wt = 5, 10, 15, 20) were then prepared by milling, and these materials were characterized with XRD, FT-IR, SEM, TEM, EDS, XPS, TGA, UV-DRS, PL, and EIS. Cu(tmipa) degraded 92.72 % of methylene blue (MB), 91.70 % of malachite green (MG), 90.62 % of methyl orange (MO), and 92.48 % of Congo red (CR) at 50, 80, 140, and 60 min, respectively. The degradation of MB with different mass fractions of Cu(tmipa)/wt%g-C3N4 was investigated and Cu(tmipa)/15 %g-C3N4 was found to have the highest efficiency (degradation of 96.24 % of MB in 30 min). The degradation rates for Cu(tmipa)/15 %g-C3N4 were 90.88 % of MG at 60 min, 90.72 % of MO at 60 min and 96.08 % of CR. The main active species for decomposition of MB, MG, MO and CR were investigated by the active species capture experiments. The formation of heterojunction between Cu(tmipa) and g-C3N4 is the main reason for the enhancement of the decomposition efficiency, which can fully absorb the visible light and effectively avoid the recombination of electrons and holes.

Design of two-dimensional coordination polymer with multiple redox-active sites for high-performance lithium-ion batteries anode material

Design of two-dimensional coordination polymer with multiple redox-active sites for high-performance lithium-ion batteries anode material

Two-dimensional coordination polymer of ytterbium(ii) with a 1,3-bis(pyridin-4-yl)propane linker

Two-dimensional coordination polymer of ytterbium(ii) with a 1,3-bis(pyridin-4-yl)propane linker

Synthesis, structure, adsorption and electrochemical properties of the new two-dimensional cobalt coordination polymer based on bifunctional ligand

Synthesis, structure, adsorption and electrochemical properties of the new two-dimensional cobalt coordination polymer based on bifunctional ligand

Ultrasound-assisted synthesis of a Eu3+-functionalized ZnII coordination polymer as a fluorescent dual detection probe for highly sensitive recognition of HgII and L-Cys

A new ZnII coordination polymer (CP) based on 2,3-pyrazine dicarboxylic acid (H2pzdc) and 4,4′-bipyridine (bpy) (ZCP) was synthesized using a facile slow evaporation method. Single-crystal X-ray diffraction revealed that ZCP is a two-dimensional porous CP, [Zn2(pzdc)2(bpy)(H2O)2] n , with van der Waals forces as the dominant interaction within its layers forming a 63 network. Employing energetic ultrasound irradiation, nanoscale ZCP (nZCP) was successfully synthesized and Eu3+ ions were incorporated within its host lattice (Eu@nZCP). The resulting platform exhibits superior fluorescence characteristics and demonstrates notable optical durability. Therefore, it was used as a dual detection fluorescent sensing platform for the detection of mercury and L-cysteine (L-Cys) in aqueous media through a turn-off/on strategy. In the turn-off process, the fluorescence emission of Eu@nZCP progressively quenches by the addition of HgII via a photo-induced electron transfer (PET) mechanism. The fluorescence of Eu@nZCP is quenched to establish a low fluorescence background through the incorporation of HgII. This devised turn-on fluorescent system is suitable for the recognition of L-Cys (based on the strong affinity of L-Cys to the HgII ion) through a quencher detachment mechanism. This method attained a relatively wide linear range, spanning from 0.001 to 25 µM, with the low detection limit of 5 nM for the sensing of HgII. Also, the corresponding limit of detection (LOD) for L-Cys is 8 nM in a relatively wide linear range, spanning from 0.001 to 40 µM.

Luminescent coordination polymers with mixed carboxylate and triazole ligands for rapid detection of chloroprene metabolite

Chloroprene is a monomer widely used in the production of neoprene, and 1-hydroxy-2-butanone (1H2B) is one of the metabolites of chloroprene in urine, which can place a significant impact on human health by disrupting the normal structure and function of DNA. Herein, a three-dimensional Zn-based coordination polymer (1) and a two-dimensional Cd-based coordination polymer (2) were synthesized with mixed ligands of 2,5-furandicarboxylic acid (H2FDA) and 1,2,4-triazole (Htrz) and fully characterized. 2 exhibits excellent stability and superior sensing performance for 1H2B with fast response within 15 s, good recyclability and a detection limit of 9.24 μM. In addition, 2 demonstrates good selectivity in presence of main coexisting compounds in urine. In-depth investigations of the sensing mechanism revealed that the luminescence sensing is based on the competitive absorption and photoelectron transfer processes.

Guest-Induced Reversible Single-Crystal-to-Single-Crystal Transformation Involving Displacement of 2D Layers and Spin Crossover Behavior Change in a Hofmann-Type Coordination Polymer.

A novel two-dimensional (2D) Hofmann-type coordination polymer, {FeII(PyHbim)2[Pd(CN)4]}·2CH3OH [1·2CH3OH, PyHbim = 2-(4-pyridyl)benzimidazole], has been synthesized, which can undergo a spontaneous guest exchange, transforming to 1·2H2O in a single-crystal-to-single-crystal (SCSC) manner, shifting from orthorhombic Cmmm to monoclinic C2/m involving the displacement of 2D layers. The solvent-induced SCSC transformation process was reversible and verified through powder X-ray diffraction (PXRD) and single-crystal X-ray crystallography analyses. Both 1·2CH3OH and 1·2H2O exhibit complete and abrupt spin crossover (SCO) behaviors in two steps, while their SCO temperature ranges drastically shift by ca.100 K, spanning room temperature, owing to different intermolecular interactions resulting from diverse interlayer packing manners and host-guest interactions. Besides, a structural phase transition is observed in 1·2CH3OH, contributing to the two-step spin transition.

Highly Specific Sulfadiazine Detection Using a Two-Dimensional Europium-Organic Coordination Polymer.

Sulfadiazine (SFZ) is an inexpensive large-consumption antibiotic used for treat bacterial infections but an excess of residues in food can be harmful. Fast and specific luminescence detection of SFZ is highly challenging because of the interference of structurally similar antibiotics. In this work, we develop a two-dimensional europium-organic coordination polymer with excellent luminescence and water stability for highly specific detection of SFZ in the range of 0-0.2 mM. Structural analysis shows that the high stability of coordination polymer is due to the high coordination number of europium ion and the special chelating coordination structure of ligand. The experiment results revealed that the high selectivity and effectively luminescence quenched behaviour of coordination polymer toward SFZ is caused by highly efficient inner filter effect.

A water stable europium coordination polymer based on mixed organic ligands as a luminescence sensor for the detection of an anthrax biomarker

The development of luminescence sensors capable of detecting anthrax biomarkers is crucial for preventing anthrax. In this study, a two-dimensional europium coordination polymer [Eu(dlba)(phen)·2(H2O)]n (CP-1) was prepared based on a rigid 1,10-phenanthroline (phen) and a flexible 2-(3,5-dicarboxybenzyloxy) benzoic acid (H3dlba) under the hydrothermal conditions. The CP-1 was characterized by powder X-ray diffraction, elemental analysis, thermogravimetric analysis, infrared spectroscopy, and single crystal X-ray diffraction. The CP-1 exhibits excellent water stability and thermal stability. Luminescence experiments demonstrated a high luminescence quenching efficiency (98.1 %) upon addition of the anthrax biomarker dipicolinic acid (DPA). Additionally, the sensor shows good sensitivity and a rapid response time of 30 s. The detection limit is as low as 0.12 µM, which is much lower than the infection dose of spores (60 µM). The sensor has a recovery rate of 95–105 % when tested on actual samples, indicating its potential for practical applications. The luminescence quenching effect may be due to the competitive absorption of DPA, which affects the efficiency of energy transfer from the ligands to the europium ions.

Facile synthesis of amorphous/crystalline Ni-Fe thiophenedicarboxylate coordination polymer nanobelts for efficient water oxidation

The oxygen evolution reaction (OER) is a complex four-electron transfer process that poses a significant challenge to the efficient production of hydrogen through water splitting. However, developing non-noble metal electrocatalyst with excellent OER performance is still a big challenge. Herein, we propose a new strategy for the in-situ growth of two-dimensional amorphous/crystalline thiophene-based Ni-Fe metal–organic frameworks (MOFs) using Ni-Fe foam (NFF) as metal source and current collector, and thiophene-2,5-dicarboxylic acid (TDC) as corrosion agent and ligand. TDC was ionized at high temperature to produce H+ ions that etch NFF to release Ni2+ and Fe2+ ions, which were coordinated with TDC to in situ synthesize two-dimensional Ni-Fe thiophenedicarboxylate coordination polymer (NiFe-TDC) nanobelts on NFF. The unique structure and synergistic effect of Ni and Fe ions of NiFe-TDC0.05 result in the excellent OER performance with an overpotential of 224 and 256 mV at current densities of 10 and 100 mA cm−2, respectively, and it can run stably for 100 h at a current density of 100 mA cm−2, indicating the outstanding stability. Furthermore, NiFe-TDC0.05 remains the excellent OER performance with an extremely low potential of 196 and 271 mV at current densities of 10 and 100 mA cm−2 in seawater with 1 mol L-1 (M) KOH, respectively. The assembled NiFe-TDC0.05 || Pt/C water electrolysis cell achieves a current density of 100 mA cm−2 at a low voltage of 1.78 V. The work provides a new method to prepare two dimensional MOFs for efficient water oxidation.

A two-dimensional coordination polymer bearing an Evans-Showell-type polyoxometalate: Synthesis, structure and biological insight†

An Evans-Showell-type polyoxometalate (POM) based coordination polymer (CP), [H2(Co2Mo10H4O38)2(Co3(L)3(HL)2(H2O)6)(HL)2]·14H2O (1), {L = 4,4′-bipyridine}, was synthesized under hydrothermal conditions and structurally characterized by infrared spectroscopy (IR), elemental analysis, powder X-ray diffraction (PXRD), diffuse reflectance spectroscopy (DRS) and single crystal X-ray diffraction methods. In 1, two [Co2Mo10H4O38]6− POMs are joined together via two Co-O interactions to form a dimer which is centrosymmetric. Here, the dimers act as repeating units and are expanded by another crystallographically independent Co ion in the structure. Binding of the cations to the O atoms of the POM and the N atoms of organic ligand resulted in the formation of a 2D CP structure. Compound 1 is the first example of an inorganic-organic polymer architecture constructed from Evans-Showell-type POM in which Co cations act as metal nodes. The topology of 1 can be rationalized as a 2D square lattice (sql) coordination network with point symbol {44.62} in which [Co2Mo10H4O38]6− and 4,4′-bipyridine units act as linkers and the Co cations as nodes. The cytotoxicity effects of the POM were evaluated on the cancer CT26 and normal L929 cell lines by an MTT assay from which an IC50 value of cancer CT26 cells of approximately 366 ppm was obtained, but normal L929 cells did not show significant toxicity.

Three multifunctional two-dimensional coordination polymers based on 1-(3-carboxybenzyl)-4,4′-bipyridinium ligand

By utilizing the carboxybenzyl viologen ligand 1-(3-carboxybenzyl)-4,4′-bipyridinium chloride (HBcbpy·Cl), 1,3,5-benzenetricarboxylic acid (H3BTC) and varying different metal ions, three new coordination polymers [Cd(Bcbpy)(HBTC)(H2O)·2H2O]n (1), [Zn(Bcbpy)(HBTC)(H2O)·2H2O]n (2) and [Co2(Bcbpy)2(HBTC)2(H2O)2·4H2O]n (3) have been synthesized and structurally characterized. Compounds 1 and 2 have identical two-dimensional (2D) coordination layered structure, while compound 3 features 2D+2D→2D structure. It is interesting that compounds 1 and 2 exhibit electron transfer photochromism, while compound 3 displays hydrochromism through dehydration. At the same time, considering the high stability and fast photo-response, the photo-modulated fluorescence and the inkless erasable printing capability are investigated.

Investigation on fluorescent sensing properties of Cd(II)-coordination polymers synthesized by nitrogen-containing carboxylic acid ligand

In this study, two-dimensional (2D) cadmium-based coordination polymer (CP) (Cd-1, [Cd4L8]n) and one-dimensional (1D) cadmium-based CP (Cd-2, [CdL(H2O)(NO3)·H2O]n) have been obtained by mixing 1-(4-benzoic acid)-3-(pyrazinyl)-1H-1,2,4-triazole (HL) as organic ligand and CdCO3 as a source of metal ions in hydrothermal/solvent-thermal reaction. The structures and properties of two examples of Cd(II) CPs were characterized and analyzed. The results from infrared spectroscopy, thermogravimetric analysis, and X-ray single-crystal diffraction analysis indicated that the CPs have a stable framework structure and better thermal stability. In addition, in the study of fluorescence properties, two Cd(II)-CPs were found to have high sensitivity to the specific recognition of Fe3+, CrO42− and Cr2O72− ions in metal nitrate and anionic aqueous solutions, and the stability and recyclability of which were further demonstrated through cycling tests, which are expected to be used for the development of the new Cd(II)-CPs and to be an excellent fluorescent probe material.

Fabrication of Substituent-Regulated Two-Dimensional Copper-Based Coordination Polymers as Urease Inhibitors

Fabrication of Substituent-Regulated Two-Dimensional Copper-Based Coordination Polymers as Urease Inhibitors