Chlorine Anions Research Articles

Chloride channels and transporters – role in the electrical activity of pacemaker and working myocardium

Chlorine anions have a significant influence on the electrophysiological properties of excitable tissues, including myocardium. Chlorine anions and transmembrane chloride currents (ICl) determine the configuration of action potentials (AP) in various regions of hearts. Disruption of transmembrane chloride transport leads to alterations in normal electrical activity, resulting in cardiac pathologies and arrhythmias. Currently, chloride conductivity and expression in the heart and a functional role have been confirmed for several types of macromolecules. These channels include CFTR, ClC-2, CaCC (TMEM16), and VRAC (LRRC8x). Additionally, chloride cotransporters (KCC, NKCC) and chloride-bicarbonate exchangers make a significant contribution to the regulation of intracellular chlorid ion concentration ([Cl-]i) and, consequently, the equilibrium potential for chloride ions (ECl). The review covers the mechanisms by which chloride transmembrane transport influences the bioelectrical activity of cardiomyocytes and the potential functions of chloride and chloride currents in specialized regions of the heart.

The embedding of 1,8-diazabicyclo[5.4.0]undec-7-ene into hyper-crosslinked ionic polymers for efficient CO2 conversion at atmospheric pressure

The preparation of cyclic carbonates via CO2 cycloaddition reaction was crucial for the lithium industry. Herein, a series of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) based hyper-crosslinked ionic polymers with different ionic site densities were prepared by simultaneously Friedel-Crafts alkylation and quaternization reactions. The obtained P[DBU]DCX(1:1) with a high ionic site density (1.45 mmol‧g−1), prepared by the equimolar ratio of 1,8-diazabicyclo[5.4.0]undec-7-ene and α,α′-dichloro-p-xylene, exhibiting excellent catalytic performance with a chloropropylene carbonate (CPC) yield of 98.8 % and selectivity of 99.3 % at atmospheric pressure. Meanwhile, the conversion capacity was comparable with other catalysts. Moreover, the CO2 cycloaddition reaction over P[DBU]DCX(1:1) catalyst followed pseudo-first-order kinetics, and the activation energy (Ea) was obtained to be 28.7 kJ/mol by performing kinetic experiments at different temperatures. In addition, it also had a good reusability and universality for different epoxides. The synergistic effects of abundant quaternary nitrogen cations derived from DBU and chlorine anions on the activation of CO2 and epoxide were explored based on density functional theory calculation. This study offers a new approach for the design and application of hyper-crosslinked ionic polymers for efficient CO2 conversion at atmospheric pressure.

Structural basis and molecular mechanisms of Cl- transmembrane transport in cardiomyocytes

The intracellular concentration of chlorine anions ([Cl-]i), the equilibrium potential for chlorine anions (ECl) and transmembrane chloride currents (ICl) are the factors that significantly influence the electrophysiological properties of excitable tissue, including the myocardium. Several types of chloride (anion) conductance have been identified in the heart. In recent years, a number of transmembrane proteins demonstrating chloride conductance have been identified (CFTR, ClC, TMEM16, LRRC8), and the expression of these macromolecules in cardiac tissue has been confirmed. Accumulated data allow for establishing a molecular substrate for some chloride anion currents (ICl,PKA, ICl,ir, ICl,vol, ICl,swell, ICl,Ca, Ito2) detected in the heart. Furthermore, the molecular mechanisms regulating [Cl-]i and ECl through chloride cotransporters (KCC, NKCC1) and chloride-bicarbonate exchangers have been established. The variety of structures determining chloride transmembrane conductivity and the complexity of molecular mechanisms regulating chloride homeostasis underlie the complex effects of activation of chloride transporters in the pacemaker, conduction system and working myocardium of the heart. This review discusses the structural, biophysical properties and molecular regulation of chloride transporter protein complexes identified in the myocardium. The review also covers the mechanisms by which chloride transmembrane transport influences the bioelectrical activity of cardiomyocytes.

Low Energy (

Benzonitrile (BZN) and carbon tetrachloride (CCl4) are versatile solvents used as a precursor for the synthesis of many products. As multi-usage molecules, these compounds may be involved in sustainable chemistry processes such as the cold plasma techniques for which the generated electrons are known to be responsible for reactions. Therefore, it is desirable to explore the interaction of low energy electrons with the co-compounds in the gas phase. The production of chlorine and cyanine anions, initiated by the electron collision with CCl4 and BZN, respectively, undergo nucleophilic substitution SN2 reaction with the precursors molecules for the synthesis of chlorobenzene and tricholoacetonitrile. The mechanism of fragmentation of benzonitrile and the synthesis reactions are rationalized by DFT calculations. The yield of the cyanine anion produced from the ion reaction increases with the temperature of the admixture gas, probed in the 25-100 °C temperature range. The present work may contribute to a potential process for the production of chlorobenzene for instance via (cold) plasma techniques.

Precision Measurement of the Electron Affinity of Chlorine via High-Resolution Photoelectron Spectroscopy.

Chlorine (Cl2) is a diatomic molecule used as an important industrial gas. However, the electron affinity (EA) of Cl2, a fundamental parameter for understanding chemical reactions, has no accurate experimental result available. The latest result of the EA value of Cl2 is 2.50(20) eV reported in 1983. In the present work, we report the precision measurement of the EA of Cl2 with the successive difference method via the high-resolution photoelectron spectroscopy of cryogenically cold chlorine anions Cl2-. The EA of Cl2 is determined to be 19432(9) cm-1 or 2.4093(11) eV.

New chloromethane preparation line for the stable chlorine isotope composition analysis*

ABSTRACT Stable isotopes of chlorine have great application potential due to the widespread occurrence of the chlorine anion in water, minerals, living organisms and the environment. In most studies, the chloride ion from the samples is converted to chloromethane, which is then analysed isotopically using a mass spectrometer. In the present study, a new design for a chloromethane preparation line is proposed. In particular, the new chloromethane preparation line uses a new system for injecting iodomethane into the preparation system, as well as ampoules with Teflon valves and the u-shaped freezers. These improvements reduced the preparation time to about 1 h, and also achieved a decent measurement uncertainty of 0.05 permil.

Tuning Properties of Layered Materials Based on Hexagonal Boron Nitride by Methylation: A Density Functional Theory Study.

In this work, the rational design of optoelectronic properties of two-dimensional materials based on hexagonal boron nitride (h-BN) by functionalization by methyl (CH3) groups is proposed. Using density functional theory, we examine the functionalization of single- or double-layer systems with either CH3 radicals alone or with both CH3 (cations) and chlorine (anions), i. e., under conditions of homolytic or heterolytic splitting of CH3Cl precursor molecules, respectively. Different degrees of methylation (coverages) are considered. The methylation of pure h-BN leads to a reduction of the band gap, while in h-BN/G heterostructures (with methylated graphene layer), methylation increases the band gap. As a consequence, h-BN/G heterostructures offer a high tunability of their optoelectronic properties. To guide possible experiments, vibrational properties and spectra of methylated h-BN and methylated h-BN/G are determined.

Оценка потенциального риска хлоридов и их влияние на всхожесть семян и развитие проростков растений

The article discusses the negative effect of de-icing materials (DM) and salts in their composition on plant seedlings germination and development. The influence of sodium and potassium cations and chlorine anion on phytotoxicity index is considered. The dynamics of test-plants (Avena sativa L., Raphanus sativa L., Hordeum vulgare L.) response on a number of test-indicators depending on the concentration of basic salts in DM by a promising method of phytotesting was analyzed. The analyzed DMs in concentrations higher than 1% have an inhibitory effect. The DM at 14–16 g/L suppresses root length of test plants (more than 50%) relative to the control. The low content of heavy metals, such as Cd, Cu, Pb, in the analyzed DM samples indicates the toxicity of sodium chloride as an active de-icing agent. The results of statistical analysis convincingly prove the high phytotoxicity of sodium chloride (NaCl) in relation to such indicators of the juvenile test-plant development as germination, the primary root length and the coleoptile height. Increasing the NaCl concentration in the solution from 0.75 to 1% was strongly toxic to the test-plants (more than 50%). Potassium chloride (KCl) in the concentration range of 0.1–1.0% showed no phytotoxicity. The KCl presence in the NaCl-included de-icing reagent reduces its phytotoxicity and allows the toxicity level of the agent to be assessed as “moderately toxic”.

Magnetic field dependence of the para-ortho conversion rate of molecular hydrogen in SABRE experiments

The use of parahydrogen – the isomer of molecular hydrogen with zero nuclear spin – is important for promising and actively developing methods for spin hyperpolarization of nuclei called parahydrogen induced polarization (PHIP). However, the dissolved parahydrogen in PHIP experiments quickly loses its spin order, resulting in the formation of orthohydrogen and reduction of the overall nuclear polarization of the substrate. This process is due to the difference of chemical shifts of hydride protons, as well as spin–spin couplings between nuclei, in the intermediate catalytic complexes, and it has not been rigorously explained so far. We proposed a new experimental technique based on magnetic field cycling for measuring the rate of molecular hydrogen para–ortho conversion in solution and applied it for non-hydrogenative PHIP Signal Amplification By Reversible Exchange (SABRE) experiments. The para–ortho conversion rate was measured over a wide range of magnetic field from 0.5 mT to 9.4 T. It was found that the conversion rate strongly depends on the magnetic field in which the reaction occurs, as well as on the concentrations of reactants. The rate decreases with increasing the concentration of pyridine ligand and increases with increasing the concentration of iridium catalyst. The model, which takes into account the reversible exchange of molecular hydrogen with the catalyst, nuclear spin–spin interaction of hydride protons with nuclei of ligands within catalytic complex and nuclear Zeeman interactions, qualitatively describes the experimental data. Two types of complexes with different spin system symmetry contribute to the molecular hydrogen conversion. In asymmetric complexes possessing hydride protons with different chemical shifts due to the presence of chlorine anion ligand the para–ortho conversion rate increases with magnetic field, while for symmetric complexes this mechanism is not operable. In the magnetic field where level anti-crossing occurs the resonant feature for the rate of para–ortho conversion is found. The results of this work can be utilized for finding the optimal conditions for obtaining the maximum hyperpolarization in the experiments employing parahydrogen.

Structure-based biological investigations on ruthenium complexes containing 2,2'-bipyridine ligands and their applications in photodynamic therapy as a potential photosensitizer.

Ruthenium complexes have been investigated for various biological applications by virtue of their radical scavenging, DNA binding, receptor binding, and cytotoxic abilities; especially the possible potential application of these complexes in photodynamic therapy (PDT). This study focuses on the synthesis, structural characterization and biological application (pertaining to its cytotoxicity and radical generation) of ruthenium complexed with salicylaldehyde fumaryl-dihydrazone (slfhH4 ), salicylaldehyde glutaryl-di-hydrazone (slfgH4 ) and 2,2'-bipyridine (bpy). During the synthesis, the anticipated complex was precipitated out but as serendipity, Ruthenium(II) tris (2,2'-bipyridyl) monochloride nonahydrate {[Ru(bpy)3 ]2+ .Cl.9H2 O} (RBMN) and Ruthenium(II) tris (2,2'-bipyridyl) monochloride septahydrate {[Ru(bpy)3 ]2+ .Cl.7H2 O}(RBMS) were crystallized from the filtrate. The crystal structure of complexes RBMN and RBMS were determined by a single-crystal X-ray diffraction methods and it showed that chlorine anion lies at the crystallographic axis and forms a halogen hydrogen-bonded organic framework (XHOF) to provide the stability. In comparison with similar structures in Cambridge Crystallographic Data Center (CCDC) revealed that the nature of the XHOF framework and the layered packing are conserved. The compounds showed excellent cytotoxic ability (against L6 cells) and the nitro blue tetrazolium (NBT) assay upon irradiation to light revealed its ability to produce reactive oxygen species (ROS). The presence of partially occupied water molecules in the layered organization within the crystal packing mimics the release of ROS resulting in cytotoxicity. The structural results together with the biological data make these complexes interesting candidates for potential photosensitizers for PDT applications.

Structural Study, Spectroscopic Characterization and Evaluation of the Antimicrobial Behavior of a New Fe (III) Organic‐Inorganic Hybrid Material: (C8H14N2)4[(FeCl6)(FeCl4)]Cl4

AbstractDue to the increasing demand for novel antimicrobials agents to treat microbial infections, the current work, focused on the synthesis of new agents owing innovative chemistry and modes of action. We describe an organic‐inorganic hybrid compound with the formula (C8H14N2)4[(FeCl6)(FeCl4)]Cl4, it was synthesized via slow evaporation at room temperature, and characterized using various techniques. The compound crystallizes in the tetragonal system, with I41/a space group. In the crystal structure, the organic layers are made up of protonated m‐Xylylene diamine (C8H14N2)2+ creating between them free tunnels, in which inorganic entities can be placed. These entities contain one octahedral (FeCl6)3− ion, one tetrahedral (FeCl4)−, and uncoordinated chlorine anions. Crystal cohesion is achieved through N−H…Cl hydrogen bonds and Cl…Cl interactions. The UV‐vis spectroscopy was investigated and the optical band gap energy 2.00 eV suggests the semiconductor behavior of the title compound. The functional groups present in the crystal structure were performed by FTIR spectroscopy. Thermal analysis was also carried out. Analysis of the Hirshfeld surface revealed that the H…Cl/Cl…H interactions dominate the structure (74 %). The new Fe(III) complex gave strong antibacterial potential against S. aureus, E. coli, M. luteus, it was able to inhibit growth of Candida species and Trichophyton intergiditale and showing lysozyme activity.

Dissociative electron attachment to 1- and 9-chloroanthracene in the gas phase

Dissociative electron attachment (DEA) to 1-chloroanthracene and 9-chloroanthracene was investigated under gas-phase conditions. In both compounds, the elimination of the chlorine anion is the dominant channel for the dissociation of molecular negative ions (NIs). The second most intense channel leads to the formation of molecular anions (Mˉ). The autodetachment lifetime of Mˉ was measured to be about 170 μs for both compounds. The widths of the Mˉ peaks indicate that molecular anions are formed via two resonances: at thermal electron energies and through a shape resonance at the energy of ∼0.5 eV. Adiabatic electron affinities were estimated in the framework of the simple Arrhenius model to be 0.86 eV for both molecules, the values being close to the theoretical predictions by DFT method of 0.90 eV and 0.93 eV for 1-chloroanthracene and 9-chloroanthracene respectively. Metastable negative ions are observed in the DEA spectra of both molecules, which testifies that the elimination of chlorine anions from molecular NIs appears on a time scale of several microseconds.

Structural Analysis and Characterization of 4-F-α-PVP Analog 4-F-3-Methyl-α- PVP Hydrochloride.

To identify 1-(4-fluorophenyl)-2-(1-pyrrolidinyl) pentan-1-one (4-F-α-PVP) analog 1-(4-fluoro-3-methyl phenyl)-2-(1-pyrrolidinyl) pentan-1-one (4-F-3-Methyl-α-PVP) hydrochloride without reference substance. The direct-injection electron ionization-mass spectrometry (EI-MS), GC-MS, electrospray ionization-high resolution mass spectrometry (ESI-HRMS), ultra-high performance liquid chromatography-high resolution tandem mass spectrometry (UPLC-HRMS/MS), nuclear magnetic resonance (NMR), ion chromatography and Fourier transform infrared spectroscopy (FTIR) were integrated utilized to achieve the structural analysis and characterization of the unknown compound in the sample, and the cleavage mechanism of the fragment ions was deduced by EI-MS and UPLC-HRMS/MS. By analyzing the direct-injection EI-MS, GC-MS, ESI-HRMS and UPLC-HRMS/MS of the compound in the samples, it was concluded that the unknown compound was a structural analog of 4-F-α-PVP, possibly with one more methyl group in the benzene ring. According to the analysis results of 1H-NMR and 13C-NMR, it was further proved that the methyl group is located at the 3-position of the benzene ring. Since the actual number of hydrogen in 1H-NMR analysis was one more than 4-F-3-Methyl-α-PVP neutral molecule, it was inferred that the compound existed in the form of salt. Ion chromatography analysis results showed that the compound contained chlorine anion (content 11.14%-11.16%), with the structural analysis of main functional group information by FTIR, the unknown compound was finally determined to be 4-F-3-Methyl-α-PVP hydrochloride. A comprehensive method using EI-MS, GC-MS, ESI-HRMS, UPLC-HRMS/MS, NMR, ion chromatography and FTIR to identify 4-F-3-Methyl-α-PVP hydrochloride in samples is established, which will be helpful for the forensic science laboratory to identify this compound or other analog compounds.

Molecular and crystal structure characteristics of 2-phenylaminotetrahydro-1,3-thiazepine hydrochloride and 2-phenyliminohexahydro-1,3-thiazepine

The current research includes the synthesis and crystallographic characterization of 2-phenylaminotetrahydro-1,3-thiazepine hydrochloride (HPAT) and 2-phenyliminohexa- hydro-1,3-thiazepine (PIT) compounds. 2-Phenylaminotetrahydro-1,3-thiazepine hydro-chloride was synthesized by cyclization of 1-(4-hydroxybutyl)-3-phenylthiourea in an acidic condition. The second compound, 2-phenyliminohexahydro-1,3-thiazepine, was obtained by neutralizing 2-phenylaminotetrahydro-1,3-thiazepine hydrochloride with sodium hydrocarbonate. Both compounds were characterized by the single-crystal X-ray diffraction method. Crystal data for C11H17N2OClS (HPAT): orthorhombic, space group P212121 (no. 19), a = 4.97183(14) Å, b = 15.1169(4) Å, c = 17.7376(5) Å, V = 1333.14(6) Å3, Z = 4, μ(CuKα) = 3.859 mm-1, Dcalc = 1.299 g/cm3, 9243 reflections measured (7.684° ≤ 2Θ ≤ 152.042°), 2749 unique (Rint = 0.0314, Rsigma = 0.0255) which were used in all calculations. The final R1 was 0.0351 (I > 2σ(I)) and wR2 was 0.0911 (all data). Crystal data for C11H14N2S (PIT): monoclinic, space group P21/n (no. 14), a = 9.6303(9) Å, b = 9.8938(6) Å, c = 11.5627(9) Å, β = 103.419(8)°, V = 1071.62(14) Å3, Z = 4, μ(CuKα) = 2.357 mm-1, Dcalc = 1.279 g/cm3, 3938 reflections measured (10.798° ≤ 2Θ ≤ 152.328°), 2172 unique (Rint = 0.0288, Rsigma = 0.0330) that were used in all calculations. The final R1 was 0.0431 (I > 2σ(I)) and wR2 was 0.1219 (all data). The asymmetric unit of HPAT contains one protonated amine, one chlorine anion, and one water molecule. Chlorine anion and water molecules play the role of the bridge in chain formation along the a- and b-axis through H-bonds with N-H hydrogen atoms. Furthermore, the Hirshfeld surface analyses are performed to determine the nature of the intermolecular contacts stabilizing the crystal structures of 2-phenylaminotetrahydro-1,3-thiazepine hydrochloride and 2-phenyliminohexahydro-1,3-thiazepine.

Negative surface charge-mediated Fe Quantum dots with N-doped graphene/Ti3C2Tx MXene as chlorine-resistance electrocatalysts for high performance seawater-based Al-air batteries

Compared to conventional alkaline Aluminum-air (Al - air) batteries, seawater-based Al-air batteries are promising large-scale energy storage devices and are highly compatible with offshore ocean locations or large-scale maritime applications. However, the complexity of the seawater components, in particular, chlorine anions (Cl−) blocks the metal surface and hinders the oxygen reduction reaction (ORR) at the cathode. Herein, we employed plasma engineering to anchor Fe Quantum dots (QDs) on a negative charge-mediated surface composed of nitrogen-doped graphene (NG) and Ti3C2Tx MXene. The negative fluorine and hydroxyl groups on MXene and NG induced strong negative-charged surface with a build-in electric field to repel Cl−, effectively protected the Fe QDs active sites from the seawater electrolyte. As a result, the cathode electrocatalysts demonstrated high ORR catalytic activity in seawater electrolytes and achieved a high-power density output of 53.6 mW/cm2 and rate performance of 0.8 V at 50 mA/cm2 in Al-air seawater batteries.

ANALYSIS OF METHODS FOR DETERMINATION OF CHLORINE DIOXIDE, CHLORITE AND CHLORATE ANIONS IN DRINKING WATER

The analysis shows that the primary measure for the purification of drinking water is its reliable disinfection with oxidants, which are chlorine and its compounds, chlorine dioxide, ozone. The aim of the article is to analyze the existing methods for determination of chlorine dioxide, chlorite, hypochlorite and chlorate anions in drinking water. To analyze the chlorine dioxide strength solutions (to control the generator performance) the iodometric method (determination of chlorine dioxide concentration, concentration of free chlorine, chlorite and chlorate anions; relative error ≤ 5%) and the method of direct absorption at 445 nm (determination of chlorine dioxide concentration in the range of concentrations of 100-700 mg / l; relative error ≤ 2%) were used. To analyze the residual concentrations of chlorine dioxide, chlorite and hypochlorite anions in their joint presence the titrimetric and photometric methods with N,N-діетил-1,4-фенилендіамінсульфатом (DFD) (error of determination is of 0.05 mg/l) were used as well as iodometric method with photometric determination of iodine at 350 nm in the concentration range 0.01-0.5 mg/l. To analyze the residual concentrations of chlorine dioxide (selective methods), such methods were used: the photometric method with chlorophenol red in the concentration range of 0.02-0.7 mg/l; relative error ≤ 5%; photometric method with chromic violet acid in the concentration range of 0.1-1.5 mg/l. The method of ion chromatography was used to analyze the residual concentrations of chlorite and chlorate anions. Given the necessity for harmonization of domestic regulatory and guidance documentation with European one, it should be considered as necessary to control chlorites and chlorates in drinking water by method of ion chromatography. It is appropriate to conduct research on the approbation of ion chromatography method for the simultaneous determination of chlorites and chlorates in samples of water after its disinfection by various oxidants (sodium hypochlorite, ozone, chlorine dioxide).

Local structure and dynamics of ions in LiCl-GdCl3, KCl-GdCl3 and LiCl-GdCl3-Gd2O3 melts: Ab initio molecular dynamics simulations and Raman spectroscopy

Currently, the novel technologies of gadolinium electrochemical production from raw oxide materials using molten oxide-salt media are being developed. To understand the phenomena, data on the structure of gadolinium-containing oxide-salt melts are required. In this study, using ab initio molecular dynamics (AIMD) and in situ Raman spectroscopy, we bring insight on local structure details and ion dynamics in these systems by the examples of LiCl–GdCl3, KCl–GdCl3 chloride melt and LiCl–GdCl3–Gd2O3 oxide-chloride melt with a Gd2O3 concentration up to 2 mol %. The Raman spectroscopy reveals the octahedral species [GdCl6]. According to the AIMD, the Gd-based groupings are joined by various numbers of shared chlorine anions. Gadolinium oxide in the chloride melt dissociates to form [Gd2OLi] groups, which are incorporated into the melt structure. The calculated self-diffusion coefficients of ions and the lifetimes of ion pairs showed that the local structure of the potassium containing melt is more stable as compared to that of the lithium containing melt, which is closely concurring with the divergence in conductivities of these melts. LiGdO2 and GdOCl phases were found in the solidified oxide-chloride melt LiCl–GdCl3–Gd2O3. It has been suggested that the complex oxide LiGdO2 is formed by the reaction Gd2O3 + LiCl → GdOCl + LiGdO2. Based on the obtained data, it was concluded that lithium-containing chloride melt should be considered not only as a solvent for gadolinium oxide, but also as an active reaction medium. Here, lithium is involved in ongoing chemical reactions and participate in reaction product.

Structural study, spectroscopic characterization, DFT calculations and electrical properties of manganese (II) organic-inorganic hybrid material (C8H14N2)2[MnCl4(H2O)2]Cl2

The new organic-inorganic compound, (C8H14N2)2[MnCl4(H2O)2]Cl2 denoted (1), crystallizes at room temperature in the monoclinic system, P21/c space group. The structure exhibits an alternate organic-inorganic layered stacking along a-axis. The inorganic layers formed by [MnCl4(H2O)2]2− anion and two uncoordinated chlorine anions. The organic layers are made of protonated m-Xylylenediamine (C8H14N2)2+. Crystal cohesion is achieved through NH…Cl and OH…Cl hydrogen bonds building up a three-dimensional network. The functional groups present in the crystal were studied by FTIR. The optical proprieties were investigated by UV-visible spectroscopy study and the electronic properties HOMO and LUMO energies were calculated by TD-DFT. Thermal behavior (DSC, DTA/TGA) was also performed, while the composition of the phase was verified by semi-quantitative analysis (EDX). Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) affirms that the structure is dominated by H…Cl/Cl…H and H…H contacts. Electrical analysis of our compound has been investigated using complex impedance spectroscopy (CIS) in frequency and temperature range 3 uHz-20 MHz and 393–443 K, respectively. Impedance spectroscopy studies show that electrical-conductivity is 1.80 10−6 S cm−1 at 443 K and the activation energy is 2.15 eV.

Layered Organic Conductors Based on BEDT-TTF and Ho, Dy, Tb Chlorides

Molecular semiconductors with lanthanide ions have been synthesized based on BEDT-TTF and lanthanide chlorides: (BEDT-TTF)2[HoCl2(H2O)6]Cl2(H2O)2 (1, which contains a 4f holmium cation), and (BEDT-TTF)2LnCl4(H2O)n (Ln = Dy, Tb, Ho (2–4), which contain 4f anions of lanthanides). Conductivity and EPR measurements have been carried out along with the SQUID magnetometry, and the crystal structure has been established for 1. The structure of 1 is characterized by an alternation of organic radical cation layers composed of BEDT-TTF chains and inorganic layers consisting of chains of the [HoCl2(H2O)6]+ cations interlinked by chlorine anions and crystallization water molecules. The magnetic susceptibility of 1–3 determined mainly by lanthanide ions follows the Curie–Weiss law with the Weiss temperatures of −3, −3, −2 K for 1–3, respectively, indicating weak antiferromagnetic coupling between paramagnetic lanthanide ions. The signals attributed to the BEDT-TTF+· radical cations only are observed in the EPR spectra of 1–3, which makes it possible to study their magnetic behavior. There are two types of chains in the organic layers of 1: the chains composed of neutral molecules and those formed by BEDT-TTF+· radical cations. As a result, uniform 1D antiferromagnetic coupling of spins is observed in the BEDT-TTF+· chains with estimated exchange interaction J = −10 K. The study of dynamic magnetic properties of 1–3 shows that these compounds are not SMMs.

Chlorine anion stabilized Cu2O/ZnO photocathode for selective CO2 reduction to CH4

Although Cu2O-based material is one of the most promising catalysts, the deactivation of surface severely limits its selectivity and stablity. Here, we present a chlorine (Cl)-modified Cu2O/ZnO heterostructure (CCZO) as photocathode with remarkable CH4 faradaic efficiency (88.6 %) and durability (over 5 h). The Cl ions in CCZO serve as a passivator to stabilize Cu2O against photo-corrosion. Stabilized Cu+ active sites promote the hydrogenation of *CO intermediate, which provides a strong driving force for CO2 reduction to CH4. Calculation results indicate that for CCZO the hydrogenation of *CO trends to form *CHO (energy barrier of 0.220 eV) rather than CO (0.344 eV), further confirming the high selectivity of CCZO to CH4. This work sheds insight on the catalytic mechanism of CCZO to modulate the energy barrier of intermediate *CO combined with H+, providing a new idea to develop high selectivity and stable catalysts for CO2 reduction.