Copper Coordination Polymers Research Articles

Hollow Calcium/Copper Bimetallic Amplifier for Cuproptosis/Paraptosis/Apoptosis Cancer Therapy via Cascade Reinforcement of Endoplasmic Reticulum Stress and Mitochondrial Dysfunction.

The endoplasmic reticulum (ER) and mitochondria are essential organelles that play crucial roles in maintaining cellular homeostasis. The simultaneous induction of ER stress and mitochondrial dysfunction represents a promising yet challenging strategy for cancer treatment. Herein, a hollow calcium-copper bimetallic nanoplatform is developed as a cascade amplifier to reinforce ER stress and mitochondrial dysfunction for breast cancer treatment. For this purpose, we report a facile method for preparing hollow CaCO3 (HCC) nanoparticles by regulating the dissolution-recrystallization process of amorphous CaCO3, and the amplifier D@HCC-CuTH is meticulously fabricated by sequentially coating disulfiram-loaded HCC nanoparticles with a copper coordination polymer and hyaluronan. In tumor cells, the dithiocarbamate-copper complex generated in situ by liberated disulfiram and Cu2+ inhibits the ubiquitin-proteasome system, causing irreversible ER stress and intracellular Ca2+ redistribution. Meanwhile, the amplifier induces mitochondrial dysfunction via triggering a self-amplifying loop of mitochondrial Ca2+ burst, and reactive oxygen species augment. Additionally, Cu2+ induces dihydrolipoamide S-acetyltransferase oligomerization in mitochondria, further exacerbating mitochondrial damage via cuproptosis. Collectively, ER stress amplification and mitochondrial dysfunction synergistically induce a cuproptosis-paraptosis-apoptosis trimodal cell death pathway, which demonstrates significant efficacy in suppressing tumor growth. This study presents a paradigm for synchronously inducing subcellular organelle disorders to boost cancer multimodal therapy.

Cu(II) Coordination Polymers for the Selective Oxidation of Biomass-Derived Veratryl Alcohol in Green Solvents: A Sustainable Catalytic Approach.

Four air-stable one-dimensional copper(II) coordination polymers (CP1-CP4) with azide linkers were synthesized using tridentate NNS and NNN ligands. Single-crystal X-ray diffraction (XRD) analysis confirmed the molecular structures of CP1, CP3, and CP4. In the presence of TEMPO, all four coordination polymers demonstrated effective catalytic activity for the selective aerobic oxidation of veratryl alcohol, a biomass model compound, under base-free conditions. CP4 exhibited the best catalytic efficiency. Oxidations were conducted at ambient temperature (40 °C) utilizing air as a sustainable oxidant. Selective oxidation of veratryl alcohol to veratraldehyde was also conducted in the presence of a catalytic amount of base (5 mol %), and enhanced reactivity was observed. The green solvents, acetone, and water, were used to maximize sustainability. The optimized reaction conditions were applied to broaden the substrate scope of various lignin model alcohols and substituted benzylic alcohols with wide electronic variability. CP4 exhibited high recyclability, consistently providing quantitative yields even after ten consecutive runs. The catalytic protocol demonstrated sustainability and environmental compatibility, as evidenced by a low E-factor (4.29) and a high Eco-scale score (90). Based on experimental evidence and theoretical calculations, a plausible catalytic cycle was proposed. Finally, the sustainability credentials of the different optimized reaction protocols were evaluated using the CHEM21 green metrics toolkit.

Highly efficient Cu(II) coordination polymer catalyst for the conversion of hazardous volatile organic compounds

Three novel coordination polymers (CPs), namely [Cu(μ-1κO,2κN-L)2]n (1), [Zn (μ-1κO,2κN-L)2(H2O)2]n (2) and [Cd (μ-1κOO’,2κN-L)2]n (3) [where HL = 4-(pyrimidin-5-ylcarbamoyl)benzoic acid], were synthesized and characterized by elemental analysis, ATR-IR, TGA, XPS and single-crystal X-ray diffraction. Despite having the same organic ligand, the various metal cations had an impact in the subsequent frameworks. Hirshfeld surface analysis was performed to investigate the intermolecular interactions and to examine the stability of the crystal structures of the three polymers. Their catalytic performances were screened for the peroxidative oxidation of Volatile Organic Compounds (VOCs), with toluene and p-xylene selected as model substrates. Tert-butyl hydroperoxide (t-BuOOH or TBHP) (aq. 70 %) was employed as the oxidant. The catalytic oxidation of toluene yielded benzyl alcohol, benzaldehyde and benzoic acid. The copper CP 1 exhibited the highest total yield for toluene oxidation, reaching approximately 36% in an aqueous medium. For p-xylene oxidation, tolualdehyde, methylbenzyl alcohol, and toluic acid were produced as the primary products, accompanied by minor ones. The experiments were conducted under diverse conditions, manipulating key parameters such as the choice of solvent (water or acetonitrile), type of oxidant (t-BuOOH or H2O2), the concentration of the oxidant and reaction temperature. In the presence of catalyst 1, a maximum total yield of ca. 80% was achieved for p-xylene oxidation.

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.

Structures, electrical properties and catecholase-like activity of a series of new copper(II) coordination polymers supported by azido bridges

A series of new copper(II)-azido complexes of 1D polymeric chains of [Cu(L1)(μ1,3-N3)]n (1) and [Cu(L2)(μ1,3-N3)]n (2), and binuclear [Cu(L3)(μ1,1-N3)]2 (3) [HL1 = N-butyl-N-(5-bromosalcylidine)ethane-1,2-diamine, HL2 = N-butyl-N-(5-chlorosalcylidine)ethane-1,2-diamine, HL3 = N-butyl-N-(salcylidine)ethane-1,2-diamine] have been synthesized and characterized. Characterizations of 1–3 have been accomplished by usual physico-chemical techniques such as elemental analysis, FTIR, UV–vis and single crystal X-ray diffraction studies. X-ray diffraction analyses of 1 and 2 reveal that the monomeric units of 1D polymers are interconnected via the μ1,3-azido bridging. The coordination geometry around the copper(II) centers in 1 and 2 can be best described as distorted square pyramidal environments. Complex 3 shows a centrosymmetric structure with two copper(II) centers that are held together by μ1,1-azido bridging in a distorted square pyramidal environment. In the electrical studies of 1–3, both direct current (dc) and alternating current (ac) analyses have been carried out based on the metal-complex (1/2/3)-metal (M-S-M) structures. The sheet resistance of the deposited films and the metal-complex contact resistance are estimated by employing transfer length method (TLM) measurements. The dark current-voltage characteristics of Al-complex (1/2/3)-Al structures are analyzed by considering dual back-to-back Schottky barrier diode structure. The voltage variations of the device current under illumination (400–700 nm) clearly demonstrate the photo-sensitivity of these materials. The catalytic activities of 1–3 have been investigated towards aerial oxidation of 3,5-di-tert-butylcatechol. All three complexes exhibit potential catalytic effectiveness towards oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butyl-o-quinone (3,5-DTBQ) with turnover numbers 14.76, 33.92 and 81.02 h−1 for 1, 2 and 3, respectively.

Synthesis, characterization, crystal structure, molecular dynamics simulations, MM-GBSA analysis, and bioactivity studies of pyrazine- and pyrimidine-modulated unsymmetrical dipyridylamide complexes

By using unsymmetrical pyrazine- and pyrimidine-modulated oligo-α-pyridylamine ligand N-(4-methylpyrimidin-2-yl)pyrazin-2-amine (Hmpmpza) (1), 1D copper(II) coordination polymer {[Cu(mpmpza)(CH3COO)](CH3OH)(H2O)}n (2) and mononuclear copper(II) complex [Cu(Hmpmpza)(NO3)2] (3) were first successfully synthesized and structurally characterized. In complex (2), Cu(II) is six-coordinated in an elongated octahedral geometry. The Hmpmpza molecule coordinates with the Cu(II) as a tridentate ligand, in which the pyrimidine and amine group nitrogen atoms link the coordination units to an infinite 1-D chain polymer. Extensive hydrogen bonds between amino groups, acetate anions, methanol, and water molecules are observed in 2, resulting in a 3D network of the 2. Complex 2 provides the first example of the complex with a modulated Hdpa ligand, in which nitrogen atoms both of the pyrazine and pyrimidine cycles participated in the coordination with the metal center. There are two crystallographically independent molecules in a mononuclear complex 3 and the Cu(II) atom is six-coordinated in an elongated octahedral geometry. Hmpmpza in complex 3 coordinates to the Cu(II) in an anti-anti conformation as a bidentate ligand. The hydrogen bonds between amino groups and coordinated nitrate anions in complex 3, link its molecules to a 1-D chain structure. However, no hydrogen bonding linkage between the 1-D chains is observed. The temperature dependence magnetic susceptibility measurement for complex 2 described by the Bonner-Fischer approximation shows a weak antiferromagnetic coupling between Cu(II) ions. The best fitting results were obtained with parameters g = 2.141, J = −0.73 cm−1 and R = 4.85 × 10−6. The molecular dynamics (MD) simulations of the 2-hAChE, 3-hAChE, 2-hBChE, and 3-hBChE complexes offer comprehensive insights into the stability and dynamic behavior of ligand-protein interactions. These findings contribute to a detailed understanding of the specific dynamics governing the stability of acetylcholinesterase and butyrylcholinesterase complexes.

Realizing Ultrasensitive and Accurate Point-of-Care Profiling for ATP with a Triple-Mode Strategy Based on the ATP-Induced Reassembly of a Copper Coordination Polymer Nanoflower.

New strategies for accurate and reliable detection of adenosine triphosphate (ATP) with portable devices are significant for biochemical analysis, while most recently reported approaches cannot satisfy the detection accuracy and independent of large instruments simultaneously, which are unsuitable for fast, simple, and on-site ATP monitoring. Herein, a unique, convenient, and label-free point-of-care sensing strategy based on novel copper coordination polymer nanoflowers (CuCPNFs) was fabricated for multimode (UV-vis, photothermal, and RGB values) onsite ATP determination with high selectivity, sensitivity, and accuracy. The resulting CuCPNFs with a 3D hierarchical structure exhibit the ATP-triggered decomposition behavior because the competitive coordination between ATP and the copper ions of CuCPNFs can result in the formation of ATP-Cu, which reveals preeminent peroxidase mimics activity and can accelerate the oxidation of 3, 3', 5, 5'-tetramethylbenzidine (TMB) to form oxTMB. During this process, the detection system displayed not only color changes but also a strong NIR laser-driven photothermal effect. Thus, the photothermal and color signal variations are easily monitored by a portable thermometer and a smartphone. This multimode point-of-care platform can meet the requirements of onsite, without bulky equipment, accuracy, and reliability all at once, greatly enhancing its application in practice and paving a new way in ATP analysis.

New hydrophilic mesoporous copper (II) coordination polymers obtained from poly(ethylene terephthalate) (PET) waste for diesel removal in water

Two new hydrophilic mesoporous copper (II) coordination polymers were synthetized from poly(ethylene terephthalate) waste by the coordination reaction under solvothermal conditions in only 60 min with quantitative yields. Both polymers and their aroyl hydrazone derivates were fully characterized by NMR (1H,13C, and 1H-15N HMBC), vibrational analysis, XPS spectroscopy, and high-resolution mass spectrometry. The XPS analysis of the new polymers 3a and 3b evidenced the formation of the N → Cu and O → Cu coordination bonds and the high-resolution mass spectrometry corroborates the presence of copper atoms in their molecular structure. The textural properties of 3a and 3b were analyzed by physisorption revealing that both materials can be classified as mesoporous materials with a pore size distribution of around 14.98 nm. Furthermore, the mesoporous copper (II) coordination polymer 3a exhibits a linear behavior with a maximum adsorption capacity of 743 and 1553 mg g−1 at 0.10 and 0.20 g/L, respectively. The adsorption/desorption cycles of 3a reveal that the novel copper (II) coordination polymers obtained from poly(ethylene terephthalate) (PET) waste had a greater adsorption capacity (1553 mg g−1); showing that structural modification of this type of coordination polymers can be a remarkable tool to increase the adsorption properties through the chemical modification to more hydrophilic, porous and crystalline coordination polymers.

Trinuclear nickel (II) string complexes and copper (II) coordination polymer with pyrazine modulated unsymmetrical dipyridylamino ligand: Synthesis, structure and bioactivity properties with molecular docking

The unsymmetrical pyrazine-modulated ligand, N-(pyridine-2-yl)pyrazin-2-amine (Hppza) (1), its 1D straight-chain copper (II) coordination polymer [Cu2(Hppza)2∙(NO3)4]n (2) and trinuclear metal string [Ni3(µ3-ppza)4Cl2] (3) and [Ni3(µ3-ppza)4(NCS)2] (4) complexes have been successfully synthesized and structurally characterized. The free ligand Hppza (1) exhibits anti-syn conformation. In an asymmetric unit of 2, there are two kinds of Cu(II) atoms, both of which have elongated octahedral coordination geometry, and the copper(II) centers are linked by oxygen atoms of one nitrate anion. There are only minor differences in Ni…Ni bond lengths between pyrazine-modulated ligand complexes of [Ni3(μ3-ppza)4×2] (X = Cl− (3), NCS− (4)) and their unmodulated analogs, while the distances between the terminal nickel atoms and the axial ligands 3 and 4 are shorter. The results of magnetic susceptibility measurements showed an antiferromagnetic exchange constant (J) of about J = –199.2 cm–1 for 3 and J = –178.0 cm–1 for 4. The electrochemical properties of nickel strings of Hppza differ significantly from their unmodulated counterparts. The activities of ligands and their metal complexes against various proteins that are AChE (PDB ID: 4M0E), BChE (PDB ID: 5NN0), α-Gly (PDB ID: 1UAS), hCA I (PDB ID: 2CAB), and hCA II (PDB ID: 3DC3) were compared, and then the ADME/T properties of molecules were examined. Afterward, the interactions occurring in the docking calculation were examined in detail with the Protein-Ligand Interaction Profiler (PLIP) service. These complexes were inhibitors of BChE, hCA I and II, α-glycosidase and AChE enzymes for complex 3 and 5 with Ki values of 12.65 and 42.95 μM for hCA I, 3.64 and 15.84 μM for hCA II, 5.44 and 50.07 μM for BChE, 15.85 and 4.77 μM for α-glycosidase and 8.58 and 86.24 μM for AChE, respectively.

Crystal structure and characterization of a new one-dimensional copper(II) coordination polymer containing a 4-amino-benzoic acid ligand.

A CuII coordination polymer, catena-poly[[[aqua-copper(II)]-bis-(μ-4-amino-benz-o-ato)-κ2 N:O;κ2 O:N] monohydrate], {[Cu(pABA)2(H2O)]·H2O}n (pABA = p-amino-benzoate, C7H4NO2 -), was synthesized and characterized. It exhibits a one-dimensional chain structure extended into a three-dimensional supra-molecular assembly through hydrogen bonds and π-π inter-actions. While the twinned crystal shows a metrically ortho-rhom-bic lattice and an apparent space group Pbcm, the true symmetry is monoclinic (space group P2/c), with disordered Cu atoms and mixed roles of water mol-ecules (aqua ligand/crystallization water). The luminescence spectrum of the complex shows an emission at 345 nm, cf. 349 nm for pABAH.

Morphology Control of Self-Assembled Copper Coordination Polymers for Glucose Assays.

Low-cost analytical assays enable accessible detection of clinically and environmentally important analytes; however, common enzyme-based assays suffer from high production and storage costs. Catalytically active synthetic materials serve as replacements for natural enzymes, but development of cost-effective, highly efficient synthetic strategies remains a challenge. Here, we utilized a facile synthesis for copper bipyridine coordination polymers (CuBpyCPs) and investigated structure-function relationships to achieve optimal catalytic properties for a glucose assay. We demonstrated the manipulation of CuBpyCP morphology, resulting in nanoscale petal-like structures and microscale high-index faceted structures, and identified three pure crystal morphologies exhibiting a comparable catalytic activity (Km = 0.3-0.5 mM) to horseradish peroxidase.

Synthesis of New Zinc and Copper Coordination Polymers Derived from Bis (Triazole) Ligands

Recent research has focused on molecules with different aromatic nitrogen-containing moieties coupled to a biphenyl core, as an effective approach for the assembly of coordination polymers. This study presents the synthesis and characterization of new ligands based on 1,1′-(3,3′-dimethoxy-[1,1′-biphenyl]-4,4′-diyl)bis(4-butyl-1H-1,2,3-triazole) (L1) and 1,1′-(3,3′-dimethoxy-[1,1′-biphenyl]-4,4′-diyl)bis(4-phenyl-1H-1,2,3-triazole) (L2) and their coordination polymers with Cu(II) and Zn(II). An unexpected coordination polymer with Cu(I) starting from Cu(II) was obtained in the case of the L2 ligand. The ligands and metal complexes underwent thorough characterization, including X-ray diffraction, NMR-, FTIR-, MS-spectrometry, and EPR, XPS, and TG-DTG analyses. While the ligand L2 generated a linear Cu(I) polymer, the ligand L1 formed a zigzag polymer with both copper and zinc.

From phosphanylphosphaalkenes to coordination copper and silver polymers containing P-P bonds.

This study was focused on the activation of the CP bond via reactions of Ph2CP-PtBu2 (1) with 1,6-hexanediol and selected dithiols (1,4-butanedithiol, 1,4-benzenedithiol and 1,4-benzenedimethanethiol). These reactions proceed according to a 1,2-addition mechanism, providing new compounds with formulas {(Ph)2(H)C-P-PtBu2}{μ2-(O-(CH2)6-O)}{tBu2P-P-C(H)(Ph)2} (2), {(Ph)2(H)C-P-PtBu2}{μ2-(S-(CH2)4-S)}{tBu2P-P-C(H)(Ph)2} (3a), {(Ph)2(H)C-P-PtBu2}{μ2-(S-C6H4-S)}{tBu2P-P-C(H)(Ph)2} (3b), and {(Ph)2(H)C-P-PtBu2}{μ2-(S-CH2-C6H4-CH2-S)}{tBu2P-P-C(H)(Ph)2} (3c). Next, the reactions of 3a and 3c with metal chlorides led to the growth of desired coordination polymers of copper(I) and silver(I). All the obtained compounds remained stable under atmospheric conditions.

Strategy for an Effective Eco-Optimized Design of Heteroleptic Cu(I) Coordination Polymers Exhibiting Thermally Activated Delayed Fluorescence.

The new series of copper(I) coordination polymers [Cu(N-N)(μ-PTA)]n[PF6]n {N-N = dmbpy (1), bpy (2), ncup (3), and phen (4)} were generated by straightforward reaction in solution or through a mechanochemical route, of [Cu(MeCN)4][PF6] with 1,3,5-triaza-7-phosphaadamantane (PTA) and the corresponding polypyridines, namely, 5,5'-dimethyl-2,2'-bipyridine (dmbpy), 2,2'-bipyridine (bpy), 2,9-dimethyl-1,10-phenanthroline (ncup), and 1,10-phenanthroline (phen). The compounds were obtained as air-stable solids and fully characterized by IR, NMR spectroscopy, and elemental analyses. The molecular structures were confirmed by single-crystal X-ray diffraction analysis (for 1, 2, and 4), revealing infinite one-dimensional (1D) linear chains driven by μ-PTA N,P-linkers. All tested Cu(I) polymeric compounds show emission at room temperature, which was attributed to thermally activated delayed fluorescence (TADF). Evidence of the involvement of the excited singlet state in the emission process is presented. Comparing the photophysical properties of 1 and 2 as well as 3 and 4, of which 1 and 3 have a stiffened structure, by introducing a methyl group to one of the ligands, we demonstrate how TADF properties depend on molecular rigidity. It is shown that stiffening of the structure reduces the flattening distortion around the Cu(I) center in the 3MLCT state. As a result, the ΔE(S1-T1) energy gap becomes smaller and the fluorescence quantum yield increases without significantly extending the emission lifetime. In particular, the ΔE(S1-T1) values for complexes 1 and 3 are among the shortest reported in the scientific literature, 253 and 337 cm-1, and the TADF lifetimes are τ(300 K) = 5.7 and 4.2 μs, respectively. The fluorescence quantum yields for these complexes are measured to be ΦPL(300 K) = 70 and 80%.

Synthesis and crystal structure of the new copper(II) coordination polymer with N1-(2-сarboxyphenyl)-N2-(4-ethylcarboxyphenyl)oxalamide ligand

A new copper (II) 1D coordination polymer (CP) of composition [9Cu·6L·4DMSO·3H2O]n has been prepared with use of N1-(2-carboxyphenyl)-N2-(4-ethylcarboxyphenyl)oxalamide as H3L ligand. The synthesis of the CP is based on a binuclear complex [Cu(H2L)2·H2O]2. A number of the [Cu(H2L)2·H2O]2 complexes were obtained as a result of exchange reaction between N1-(2-carboxyphenyl)-N2-(aryl)oxalamide triethylammonium salts (HEt3N+·(H2L)-) and CuCl2·2H2O in an aqueous medium.

Copper coordination polymer with lattice water molecules and strong electrocatalytic OER activity

The versatility of organic ligand and metal coordination geometry produced coordination polymer with intriguing network structure and exciting functional properties. Herein, we have synthesized a copper coordination polymer (Cu-HS) using an amino acid based multidentate ligand and explored its electrocatalytic OER activity in alkaline condition. Single crystal structural studies showed the formation of 1D coordination network structure and inclusion of lattice water. Copper ions in Cu-HS displayed octahedral and square pyramidal coordination geometry. Electrocatalytic OER studies in alkaline medium showed strongly enhanced activity for Cu-HS polymer that required an overpotential of 273 mV to achieve the benchmark current density of 10 mA/cm2. Tafel slope analysis and electrochemical impedance studies suggested faster reaction kinetics at the electrode surface modified using Cu-HS. After catalysis, XPS and FTIR spectra of Cu-HS suggested the conversion to metal oxide during the electrocatalysis.

Copper(II) and Zinc(II) coordination polymers based on glutaric acid and 1,2-bis(4-pyridyl)ethylene: Hydrothermal synthesis, characterization and thermal behaviors

1,2-bis(4-pyridyl)ethylene (dpe) and glutaric acid (H2glu) with Cu(II) and Zn(II) afforded two coordination polymers namely, [Cu(µ3-glu)(µ-dpe)]n (1) and [Zn(µ3-glu)(µ-dpe)0.5]n (2), and they were characterized by elemental analysis, IR spectroscopies, single crystal X-ray diffraction and powder X-ray diffraction (PXRD) techniques. X-ray diffraction studies have shown that complex 1 crystallizes in the triclinic system, in the P-1 space group, while complex 2 crystallizes in the C2/c space group in the monoclinic system. In complexes 1 and 2, the glu ligand adopts tetradentate coordination mode that one carboxylate group bidentate, other carboxylate group bis(monodentate)-bridging. Complex 1 displayed 2D network with {44.62} point symbol and sql topology which is extended into a 3D supramolecular framework by C−H⋯O hydrogen bonds interactions. Complex 2 featured a 3D network that two identical 3D self-penetrating frameworks interpenetrate each other in a 2-fold (3D+3D →3D) mode, with a pcu; 6/4/c1; sqc1 topology with the point symbol of {412.63}. The optical band gap energy values calculated by the Kubelka–Munk function for 1 and 2 observed at 3.20 and 3.24 eV, respectively. Moreover, the thermal properties of the complexes were investigated in the study.

Selective Gas Sensing under a Mixed Gas Flow with a One-Dimensional Copper Coordination Polymer.

Structural changes of the coordination polymer associated with gas adsorption (gate opening-type adsorption) can be linked to bulk physical properties such as magnetism, electrical conductivity, and dielectric properties. To enable real-space sensing applications, it is imperative to have a system where the selective adsorption of mixed gases can be correlated with physical properties. In this report, we demonstrate that a crystalline sample of one-dimensional (1D) coordination polymer exhibits selective CO2 adsorption while simultaneously displaying dielectric switching behavior in a mixed N2/CO2 gas environment. In the crystal of {[Cu2(2-TPA)4(pz)]·CH3CN}n (1·CH3CN), where 2-TPA and pz are 2-thiophencarboxylate and pyrazine, respectively, paddle wheel-type units of [Cu2(2-TPA)4] are bridged by pz, forming a 1D chain structure. One of the two crystallographically independent 2-TPA units was interacted with the pz moiety of the adjacent 1D chain by π···π interactions, forming a two-dimensional (2D) layer parallel to the ab plane. Activated 1 shows selective CO2 adsorption by a gate opening-type adsorption mechanism, indicating that the CO2 adsorption process is accompanied by a structural change. The change in the real part of dielectric permittivity (ε') under the mixed N2/CO2 gas flow is a result of the selective CO2 adsorption, which was supported by the enthalpy changes (ΔH) associated with CO2 adsorption in two methods: CO2 adsorption isotherms and temperature-dependent measurements of ε' under a mixed N2/CO2 gas flow. The calculated ΔH values were found to be in good agreement across both methods. The CO2 ratio in the mixed N2/CO2 gas flow increased, and the switching ratio of ε' (Δε') also increased. Notably, Δε' exhibited a marked increase beyond the pressure required for gate opening adsorption.

Synthesis of hydrogen bonded copper(II) coordination polymer: Photocatalytic degradation of Rose Bengal dye and luminescent sensing of Hg+2, Cr2O72−, and nitrofurantoin

A new helical coordination polymer, [Cu(Or)(H2O)3]n (KA@CP-ARS) has been synthesized at room temperature and examined using single-crystal X-ray diffraction (SC-XRD) and other analytical techniques. KA@CP-ARS formed 1D helical type structure via coordination bonding as well as a 3D supramolecular network through hydrogen bonding interactions. KA@CP-ARS manifested as a remarkable luminescent sensor for volatile organic compounds (VOCs), 3-Nitrophenol, Cr2O72−, Hg2+, creatinine, nitrofurantoin and sucrose (200 mg/dl) in particular along with the remarkable photocatalytic degradation of Rose Bengal (RB) dye with 96.54% efficiency. Overall this study demonstrates that the synthesized Cu-orotate coordination polymer has good luminescent sensing and catalytic degradation activity, therefore could be employed for a range of applications such as sensing of biomolecules like sucrose and photocatalysis of toxic dyes.

A 3D copper (II) coordination polymer based on sulfanilic acid ligand (CP 1) for efficient biomolecular interaction with bovine serum albumin: spectroscopic, molecular modelling and DFT analysis

Several biochemical reactions occur during the interaction of metal complexes and proteins due to conformational modifications in the structure of the protein, which provide fundamental knowledge of the effect, mechanism, and transport of many drugs throughout the body. Here, we report the synthesis, identification, and impact of the 3-dimensional Copper(II)sulfanilic acid coordination polymer (CP 1) on interactions with bovine serum albumin (BSA). The CP 1 was synthesized via a simple hot stirring method, and the single crystal XRD confirms the effective bonding interactions between metal and organic ligand, forming a crystalline polymeric chain and the topological study shows the sql type of underlying net topology. Powder XRD, Fourier transform infrared spectroscopy, and thermogravimetric analysis were also performed. Moreover, DFT/B3LYP calculations provide chemical precision for the resulting complex. Further, the changes that occur in the secondary structure of protein when CP 1 binds with BSA as well as its binding capacity were investigated via circular dichroism analysis and spectroscopic methods such as UV-absorption spectroscopy and fluorescence spectroscopy, respectively. The CP 1/BSA complex melting point was also measured, and its temperature-dependent heat denaturation was studied along with molecular docking. Communicated by Ramaswamy H. Sarma