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We investigate attachment of slow electrons (0–10 eV) to naphthalene (Np) clusters in a crossed beam experiment. Supersonic expansions under different conditions using different buffer gases generate the clusters: in He, Ne, and low pressure Ar, neat (Np)N clusters are formed, while we also observe mixed clusters of naphthalene with rare-gas atoms in co-expansion with Ar above 0.5 bar and with Kr. Negatively charged (Np) n − and Rg m (Np) n − (Rg = Ar, Kr) clusters are analyzed by mass spectrometry, and electron energy dependent ion yields are measured. We show that the smallest stable naphthalene complex with an excess electron, the dimer (Np) 2 − anion, cannot be formed in a binary collision of a free electron with (Np)2 dimer, nor with (Np)3 trimer. Evaporation of a weakly bound Ar atom(s) from a mixed ArM(Np)2 cluster following electron attachment leads to the dimer (Np) 2 − anion. Larger (Np) n − , n > 3, transient cluster anions decay via evaporation of an Np unit on a timescale of tens of microseconds. The self-scavenging process opens around 6 eV, where a naphthalene unit is electronically excited by the incoming electron, which is slowed down and trapped. However, the transient negative ion is efficiently stabilized only in the mixed clusters, from which Ar atom(s) can be evaporated. [ABSTRACT FROM AUTHOR]

Low-energy (0–14 eV) resonance electron interaction and fragment species produced by dissociative electron attachment (DEA) for enantiomeric forms of glutamic acid (Glu) are studied under gas-phase conditions by means of DEA spectroscopy and density functional theory calculations. Contrary to a series of amino acids studied earlier employing the DEA technique, the most abundant species are not associated with the elimination of a hydrogen atom from the parent molecular negative ion. Besides this less intense closed-shell [Glu – H]– fragment, only two mass-selected negative ions, [Glu – 19]– and [Glu – 76]–, are detected within the same electron energy region, with the yield maximum observed at around 0.9 eV. This value matches well the energy of vertical electron attachment into the lowest normally empty π* COOH molecular orbital of Glu located at 0.88 eV according to the present B3LYP/6-31G(d) calculations. Although the detection of asymmetric DEA properties a priori is not accessible under the present experimental conditions, "chirality non-conservation" can be associated with some decay channels. Evidently, the measured spectra for the L- and D-forms are found to be identical, the results, nevertheless, being of interest for the forthcoming experiments utilizing spin-polarized electron beam as a chiral factor in the framework of conventional DEA technique. [ABSTRACT FROM AUTHOR]

Mass transport in bulk spinel ferrites NiFe2O4 is studied computationally using the kinetic activation–relaxation technique (k-ART), an off-lattice kinetic Monte Carlo algorithm. Diffusion mechanisms—difficult to observe with molecular dynamics—are described by k-ART. Point defects are assumed to be responsible for ionic diffusion; thus, both cation and anion defects are investigated. This work focuses on vacancies and interstitials by comparing their properties with two Buckingham potential parameterizations: one with nominal charges and the other with partial charges. Both potentials are corrected at short distances, thus allowing interstitial diffusion and avoiding the catastrophic infinite energies appearing with Buckingham at short distances. The energy landscape along different pathways is described in detail. Both potentials predict the same mechanisms but different migration energies. Mechanisms by which a normal spinel is transformed to an inverse spinel via cation diffusion are unveiled, and diffusion coefficients are predicted. We find that interstitial Ni diffusion involves the movement of two Ni ions and that O interstitials trigger a collective diffusion of O ions, while an O vacancy diffuses by an O ion moving to the center of a cuboctahedron. [ABSTRACT FROM AUTHOR]

The mutual synergistic regulation of the multi-functional sites on a single receptor molecule for ion-binding/recognition is vital for the new receptor design and needs to be well explored from experiment and theory. In this work, a new macrocyclic ion receptor (BEBUR) with three functional zones, including two ether holes and one biurea groups, is designed expecting to mutually enhance the ion-binding performance. The binding behaviors of BEBUR mainly for Cl− and Cs+ are deeply investigated by using density functional theoretical calculations. It is found that Cl−/Cs+ binding can be mutually enhanced and synergistically regulated via corresponding conformational changes of the receptor, well reflecting an electrical complementary matching and mutual reinforcement effect. Moreover, solvent effect calculations indicate that BEBUR may be an excellent candidate structure for Cl−-binding with the enhancement of counter ion (Cs+) in water and toluene. In addition, visualization of intermolecular noncovalent interaction is used for analysis on the nature of the binding interactions between receptor and ions. [ABSTRACT FROM AUTHOR]

A double harmonic oscillator model is applied to compute the negative ion photoelectron spectra (NIPES) of the 1- and 2-cyanonaphthalene (CNN) radical anions. The computed Franck–Condon factors utilize optimized structures and harmonic vibrational frequencies obtained using density functional theory with the B3LYP 6-311++G (2d,2p) basis set while considering the mode-mixing Duschinsky effects. To test the accuracy of our model, the NIPES of α and β naphthyl radical anions were computed, and a strong agreement between the slow electron velocity-map ion imaging spectra and the predicted spectra was found. The adiabatic electron affinities (EAs) of the ground singlet states (S0) in 1-CNN and 2-CNN are 0.856 and 0.798 eV, respectively. The origin of the lowest-lying triplet (T1) states in 1-CNN and 2-CNN is found to be 3.226 and 3.266 eV, resulting in singlet–triplet energy splittings (ΔEST) of 2.370 and 2.468 eV, respectively. Both the NIPES for electron detachment to the S0 and T1 states exhibit well-resolved vibrational features, allowing for the assignment of several vibrational fundamental frequencies. Following deprotonation, several isomers are formed, with the most stable deprotonated radical anions in 1-CNN and 2-CNN, corresponding to the removal of the most acidic proton, with EAs of 2.062 and 2.16 eV. The rich spectroscopic and thermochemical data obtained in the current study make the CNN radical anions and their deprotonated species interesting systems for investigation in gas-phase, negative-ion experiments. [ABSTRACT FROM AUTHOR]

The dielectric constant is a critical parameter in many energy-related applications. Typically, increasing the dielectric constant of soft materials involves adding high dielectric constant polar liquids or inorganic fillers, but there are limitations to this approach due to safety concerns with volatile and flammable solvents and the agglomeration of inorganic fillers. An alternative approach is to add zwitterionic liquids that exhibit exceptionally high dielectric constants with negligible volatility. Here, we report the synthesis of a series of zwitterionic liquids containing an imidazolium cation, exhibiting the highest dielectric constant among all organic molecules (∼350 at 293 K). The cation–anion linkage was tailored in a wide range between three and nine carbons, rendering the zwitterion dipole from 25 to 52 D. Comparing the dielectric constant for zwitterions with different anions (i.e., sulfonylimide, sulfonate, and carboxylate) reveals the beneficial impacts of the delocalized sulfonylimide anion vs the carboxylate anion due to the enlarged molecular dipole and more homogenous liquid morphology. Molecular dipole and liquid morphology are identified as the keys to developing high dielectric constant zwitterionic liquids. The extremely high dielectric constant accessible with the proposed molecular design paves new avenues for developing high dielectric constant zwitterions that act as dielectricizers. [ABSTRACT FROM AUTHOR]

The plasma-wall transition is investigated by a one-dimensional steady-state multifluid model, which was presented in detail in Part I [T. Gyergyek et al., AIP Adv. 14, 045201 (2024)]. In this work, the plasma-wall transition is analyzed for the case where the plasma consists of singly charged positive ions, electrons, and singly charged negative ions. When the temperature and initial density of the negative ions are varied, a transition between two types of solutions of the model is observed. We call them the low and high solution, with respect to the absolute value of the potential drop. When the density and temperature of the negative ions are above a critical value, the low solution is observed. As the mass of the positive ions increases, these critical values also increase, but only until the ion mass is below about 1000 electron masses. With larger ion masses, the critical density of the negative ions and the temperature no longer change. In the low solution, the potential drop in front of the sheath is determined by the negative ions and is smaller in absolute terms than in the case of the high solution, where the potential drop in front of the sheath is determined by the electrons. If the problem is analyzed on the pre-sheath scale, the transition between the low and high solution is very sharp. However, when the neutrality condition is replaced by the Poisson equation, this transition becomes blurred and the solutions of the model equations exhibit oscillations. The role of the smallness parameter is highlighted. It is shown how the initial electric field is determined. Deviation of the negative ion density profile from the Boltzmann relation is discussed. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) are common atmospheric pollutants, and they are also ubiquitous in the interstellar medium. Here, we report the study of a complex O-containing PAH anion, the deprotonated 2-hydroxytriphenylene (2-OtPh–), using high-resolution photoelectron imaging and photodetachment spectroscopy of cryogenically cooled anions. Vibrationally resolved photoelectron spectra yield the electron affinity of the 2-OtPh radical as 2.629(1) eV and several vibrational frequencies for its ground electronic state. Photodetachment spectroscopy reveals bound valence excited electronic states for the 2-OtPh– anion, with unprecedentedly rich vibronic features. Evidence is presented for a low-lying triplet state (T1) and two singlet states (S1 and S2) below the detachment threshold. Single-color resonant two-photon photoelectron spectroscopy uncovers rich photophysics for the 2-OtPh– anion, including vibrational relaxation in S1, internal conversion to the ground state of 2-OtPh–, intersystem crossing from S2 to T1, and a long-lived autodetaching shape resonance about 1.3 eV above the detachment threshold. The rich electronic structure and photophysics afforded by the current study suggest that 2-OtPh– would be an interesting system for pump–probe experiments to unravel the dynamics of the excited states of this complex PAH anion. [ABSTRACT FROM AUTHOR]

The energetic stability of positron–dianion systems [A−; e+; A−] is studied via many-body theory, where A− includes H−, F−, Cl−, and the molecular anions (CN)− and (NCO)−. Specifically, the energy of the system as a function of ionic separation is determined by solving the Dyson equation for the positron in the field of the two anions using a positron–anion self-energy as constructed in Hofierka et al. [Nature 606, 688 (2022)] that accounts for correlations, including polarization, screening, and virtual-positronium formation. Calculations are performed for a positron interacting with H 2 2 − , F 2 2 − , and Cl 2 2 − and are found to be in good agreement with previous theory. In particular, we confirm the presence of two minima in the potential energy of the [H−; e+; H−] system with respect to ionic separation: a positronically bonded [H−; e+; H−] local minimum at ionic separations r ∼ 3.4 Å and a global minimum at smaller ionic separations r ≲ 1.6 Å that gives overall instability of the system with respect to dissociation into a H2 molecule and a positronium negative ion, Ps−. The first predictions are made for positronic bonding in dianions consisting of molecular anionic fragments, specifically for (CN) 2 2 − and (NCO) 2 2 − . In all cases, we find that the molecules formed by the creation of a positronic bond are stable relative to dissociation into A− and e+A− (positron bound to a single anion), with bond energies on the order of 1 eV and bond lengths on the order of several ångstroms. [ABSTRACT FROM AUTHOR]

Electron-driven processes in isolated curcumin (CUR) molecules are studied by means of dissociative electron attachment (DEA) spectroscopy under gas-phase conditions. Elementary photostimulated reactions initiated in CUR molecules under UV irradiation are studied using the chemically induced dynamic nuclear polarization method in an acetonitrile solvent. Density functional theory is applied to elucidate the energetics of fragmentation of CUR by low-energy (0–15 eV) resonance electron attachment and to characterize various CUR radical forms. The adiabatic electron affinity of CUR molecule is experimentally estimated to be about 1 eV. An extra electron attachment to the π1* LUMO and π2* molecular orbitals is responsible for the most intense DEA signals observed at thermal electron energy. The most abundant long-lived (hundreds of micro- to milliseconds) molecular negative ions CUR– are detected not only at the thermal energy of incident electrons but also at 0.6 eV, which is due to the formation of the π3* and π4* temporary negative ion states predicted to lie around 1 eV. Proton-assisted electron transfer between CUR molecules is registered under UV irradiation. The formation of both radical-anions and radical-cations of CUR is found to be more favorable in its enol form. The present findings shed some light on the elementary processes triggered in CUR by electrons and photons and, therefore, can be useful to understand the molecular mechanisms responsible for a variety of biological effects produced by CUR. [ABSTRACT FROM AUTHOR]

In this work, we report a rare ionic covalent organic framework (named as ECUT-iCOF-5) synthesized by the Knoevenagel reaction using an ionic liquid monomer. ECUT-iCOF-5 is found to show a promising potential for gold extraction with a high extraction ability towards gold, including a high extraction capacity (3260 mg g−1), good selectivity over both cations and anions, and good recycle use (at least six times). [ABSTRACT FROM AUTHOR]

A base-catalyzed O-phosphorylation of aldehyde/ketone with RP-menthyl phenylphosphinate afforded phosphonates. The mechanism was proposed as an intermolecular SN@P reaction of α-hydroxy phosphinate. In an intermediate, the C–P bond was transferred from the equatorial to axial position via Berry pseudorotation, and then was cleaved with the leaving of a carbon anion. The P-retention and C-racemization could be satisfactorily explained by the mechanism. [ABSTRACT FROM AUTHOR]

Gradient refractive index microlens arrays (GRIN MLAs), covering the visible to mid-infrared wavelength range, are imprinted in GeS 2 -Ga 2 S 3 -CsX (X = Cl, Br, and I) chalcohalide glasses by an efficient and economical microthermal poling process. This study investigates the impact of anodic mesh number (ranging from 400 to 2000 mesh) and halogen anions on the optical properties, including focal length, resolution, and aberration. Findings reveal that as the mesh number decreases, the focal length and aberration of GRIN MLAs increase. Optimal resolution is achieved with the 500 mesh sample, which also shows the best phase difference performance. The migration depth of Cs+ ions, influenced by halogen anions (from Cl to I), results in contrasting optical properties between lower mesh (400–750) and higher mesh (1000–2000) samples. Notably, the Cl-500 GRIN MLAs demonstrate a focal length of 615.0 μm, a maximum resolution of 6.35 lp/mm, and minimal aberration of −0.0591. These changes are attributed to the predominant transverse and longitudinal migration of Cs+ ions in mesh square areas. This research highlights the relationship between microthermal poling conditions, ion migration, and optical performance, providing valuable insights for the application of GRIN MLAs in advanced optical systems. [ABSTRACT FROM AUTHOR]

Photo‐regulated transmembrane ionophores enable spatial and temporal control over activity, offering promise as targeted therapeutics. Key to such applications is control using bio‐compatible visible light. Herein, we report red‐shifted azobenzene‐derived synthetic anionophores that use amber or red light to trigger (E)‐(Z) photoisomerisation and activation of transmembrane chloride transport. We demonstrate that by tuning the thermal half‐life of the more active, but thermodynamically unstable, Z isomer to relax on the timescale of minutes, transient activation of ion transport can be achieved by activating solely with visible light and deactivating by thermal relaxation. [ABSTRACT FROM AUTHOR]

Exploring the connections between the ion substitution of a material, its crystal structure, and its performance in applications is a regular task in synthetic chemistry. However, there still remain major challenges in the substitution of polyanionic groups for single ions. Herein, a strategy of channel species substitution of single anions by polyanionic groups in a zeotype rigid framework to design a new deep-ultraviolet nonlinear zincophosphate, {[Li3Na3(SiF6)]Cs2}[(ZnPO4)6], and tune physicochemical properties was proposed. [ABSTRACT FROM AUTHOR]

Pb-based chalcogenides display abundant structural diversity and distinguished properties. Based on a mixed anion and dimensional reduction combined strategy, a wide band gap Pb-based thiohalide, Pb6Ba3Si2S8I10, has been rationally designed and synthesized experimentally by the flux method. The compound crystallizes in the R3¯c space group with cell parameters a = 9.7925(2) Å, b = 9.7925(2) Å, and c = 70.628(3) Å and is composed of [SiS4] tetrahedra and unprecedented [PbI5S2] polyhedral units, resulting in a unique quasi-two-dimensional structure, which enriches the chemical and structural diversity of Pb-based thiohalides. The experimental band gap of Pb6Ba3Si2S8I10 was determined to be 2.80 eV. Based on statistical analyses and to the best of our knowledge, it is the largest experimental optical band gap among the known Pb-based thiohalides. The results demonstrate the feasibility of using highly electropositive Ba atoms to regulate the dimensions of the structural framework of thiohalides and give new insights into the structure and property modifications of thiohalides by the mixed anion and dimensional reduction combined strategy. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Poly‐NHC‐based organometallic assemblies 3‐PF6, 3‐SbF6 and 3‐OTf were obtained and verified by NMR spectroscopy, ESI mass spectrometry and single‐crystal X‐ray diffraction analyses. Controllable structural interconversion was observed between the poly‐NHC‐based organometallic assemblies and their self‐aggregated dimers in solution affected by concentration, solvent and metal ion. 1H NMR spectra of assembly 3‐PF6 in CD3CN at different concentrations demonstrated controllable structural interconversion, and 19F NMR spectrum of assembly 3‐PF6 at high concentration further evidenced the presence of the free hexafluorophosphate anion and encapsulated hexafluorophosphate anion for its two sets of signals. In addition, single‐crystal X‐ray diffraction analysis provided clear evidence that in the solid state, two assemblies 3‐PF6 were vertically stuck, forming a self‐aggregated dimer with an encapsulated hexafluorophosphate anion. Investigating the reversible structural interconversion is beneficial for revealing the intrinsic nature on the atom level and paving the way to design the stimuli‐responsive functional system. [ABSTRACT FROM AUTHOR]

ABSTRACT Two new luminescent metal–organic frameworks (MOFs), namely, [Zn2(HL)2]n (1) and {[Cd2(HL)2(H2O)2]⋅(H2O)0.5}n (2) [H3L = 5‐((4‐(1H‐1,2,4‐triazol‐1‐yl)benzyl)amino)isophthalic acid ligand], have been solvothermally synthesized and characterized. Single‐crystal x‐ray diffraction shows that 1 exhibits a 3D framework, whereas 2 features 2D network. Furthermore, the fluorescence studies demonstrated that 1 and 2 exhibited luminescent sensing activity for nitrobenzene (NB), Fe3+ ions, and Cr2O72− anions with high selectivity, high sensitivity, and low detection limit, the corresponding detection limits of 1 were 6.40 × 10−7, 1.26 × 10−7, and 1.44 × 10−7 M, respectively, and that of 2 were 2.42 × 10−6, 3.41 × 10−7, and 2.90 × 10−7 M, respectively. 1 and 2 exhibited excellent solvent, pH, and thermal stabilities. The results suggested that both 1 and 2 can be considered as potential fluorescent sensors of NB, Fe3+ ions, and Cr2O72− anions. [ABSTRACT FROM AUTHOR]

The chemical components of natural fragrant plant extracts are of high complexity, and the strategies for quality control (QC) and further discovery of fragrance mechanisms still need to be further investigated. This study integrated the strategies and methods of untargeted metabolomics and chemometrics and statistical modeling to attain the goal. The techniques of reversed-phase and HILIC analysis of ultra-performance liquid chromatography-high-resolution mass spectrometry (UPLC-HRMS) were simultaneously used to collect data in both positive and negative ion modes. The pattern analysis of fingerprints and discovery of characteristic molecular markers for QC analysis were comprehensively employed to reach in-depth analysis of the quality variation and discovery of differential molecules among natural fragrant plant extracts. The former uses fingerprint technique to analyze their overall similarities and differences, and the latter comprehensively discovers molecular substances characterizing the chemical characteristics of fragrant extracts with the help of metabolomics and univariate and multivariate methods. The findings are expected to be used as the molecular markers in product manufacturing, sales, and consumption to achieve accurate quality control and recognition of targeted molecules for potential quality monitoring using spectroscopy techniques. In this work, 27 natural fragrant extracts were applied as examples, and their chemical components were comprehensively analyzed with discovery of markers for quality control. After data integration, 1178 molecules were annotated, and 267 differential metabolite molecules with the values of variable importance in the projection (VIP) larger than 1.0 were found. The results show that the method proposed in this work is of great significance for high-coverage analysis, QC marker discovery, and aroma mechanism elucidation, which has potential applications in the areas of food, cosmetics, pharmaceuticals, tobacco, and others. [ABSTRACT FROM AUTHOR]

Decades of research unveiled the unlimited potential of metal–organic frameworks (MOFs). Nevertheless, the hazardous and expensive production involving massive amounts of organic solvents has severely limited their widespread industrial adoption. Herein, the advantages of two eco-friendly strategies, base-assisted synthesis and modulated hydrothermal chemistry, were complementarily integrated, with the acetate anion introduced as a mild and efficacious modulator to regulate the coordination and tailor the crystallization pathway(s). The green, rapid, and scalable synthesis of a dual-ligand Zn-MOF was thereby achieved in water media, featuring an unprecedented space–time yield of 24 ton per m3 per day and a batch size exceeding a kilogram (i.e., 1.2 kg). Owing to its strong affinity toward CH4, the acquired Zn-MOF demonstrated a considerable CH4/N2 separation capacity under ambient conditions. This study not only facilitates the green and scalable production of MOFs but also offers a cost-effective adsorbent for CH4 recovery. [ABSTRACT FROM AUTHOR]

Constructing multifunctional films using layered rare earth (RE) hydroxide (LRH) nanosheets as building blocks is a popular topic. The traditional synthesis of LRH films involves four main steps: bulk crystal synthesis, intercalation of long-chain organic anions, exfoliation, and layer-by-layer self-assembly into a film. In this work, the layered gadolinium hydroxide (LGdH) film was directly synthesized via electrodeposition within 10 minutes. The effects of the synthesis conditions, including working voltage, concentration of nitrate solution, and the reaction temperature, on the structural characteristics and morphologies were investigated. In order to improve the photoluminescence performance of LGdH:RE films, the quenching groups in the LGdH structure were removed/replaced via appropriate heat treatment/anion exchange with MoO42−, based on the thermal behaviour/anion exchange properties of the LGdH, and Gd2O3:RE/NaGd(MoO4)2:RE films with enhanced photoluminescence and stability were obtained. The electrodeposition combined with heat treatment/anion exchange techniques established in this study led to the rapid synthesis of Gd2O3:RE/NaGd(MoO4)2:RE films, and could have wide implications for the generation of other types of inorganic functional films. [ABSTRACT FROM AUTHOR]

Heterometallic actinide compounds with tailored components functions have attracted much attention, but their controllable synthesis is still challenging. In this work, using bulky transition metal‐bipyridine cations as structure directing components, we have successfully synthesized six novel heterometallic uranyl squarate compounds, 1–6 with different metal‐bipyridine units. A time‐dependent crystal transformation from 1 with triple interwoven structure to 2 with parallel stacked structure is observed within the observation period of one month and further characterized via single‐crystal X‐ray diffraction (SCXRD) and powder X‐ray diffraction (PXRD). Further evidences from a combination of several techniques including thermal analysis, variable‐temperature PXRD and variable‐temperature SCXRD demonstrate dehydration‐related lattice evolution of 1 on the basis of structural flexibility of 1, which could be the origin of above‐mentioned crystal transformation from 1 to 2. Furthermore, the effect of types of anions (NO3−, Cl−, and SO42−) on structural diversity of 1–6 is also discussed in detail, where the Cl− or NO3− ion coordinate to Cu2+ center in isostructural 3 and 4, while SO42− bonds to uranyl nodes in isostructural 5 and 6. This work provides a feasible method for the tailored synthesis of multicomponent actinide complexes by the involvement of bulky charge balance components. [ABSTRACT FROM AUTHOR]

A hybrid receptor‐sensor for anions originating from the merging of positively charged ammonium moieties for electrostatic attraction/stronger binding of azacrowns with directionality of calixpyrrole hydrogen bond donors for selectivity is investigated. As demonstrated this hybrid receptor‐sensor shows a remarkable selectivity for orthophosphate even in the presence of other phosphates and anions found in cellular materials (Kassoc H2PO4−>H2P2O72−>AMP−≫ADP2− or ATP3− over halides, nitrate, or hydrogen sulfate; all Na+ salts in water) but also cellular polyphosphate or phospholipids. This selectivity is harnessed in a real‐time monitoring of cell lysis by lysozyme, which releases orthophosphate and other phosphates and anions from the cells. This sensitive (LOD 0.4 μM) fluorescence‐based microscale method compares favorably with the state‐of‐the‐art techniques but can easily be practiced in a high‐throughput screening (HTS) manner. The anion binding and selectivity in aqueous solutions were investigated by NMR and put in context with phosphate binding of the parent calix[4]pyrrole. The microscopic understanding of anion binding by the hybrid receptor was then obtained from a combination of density functional theory (DFT), classical molecular dynamics (MD) with explicit water solvation, and ab initio MD (AIMD) simulations. Correlating the NMR and fluorescence binding data with studies of solvation of the receptor, phosphate anion, and the resulting complex confirms the binding is largely driven by entropic component (TΔS) associated with receptor and anion desolvation. [ABSTRACT FROM AUTHOR]

In situ formed gel polymer electrolytes (GPEs) have advantages in safety and adaptability to current high‐voltage lithium‐ion batteries (LIBs). However, it is challenging for GPEs to achieve stable cycling at high current densities. A flexible framework is proposed for stable in situ GPE, by introducing ─CF3 groups to the polymer network to establish rapid Li+ transport channels, and incorporating secondary amine N─H groups to anchor anion. The obtained GPE exhibits a high ionic conductivity of 2.6 mS cm−1 and a high Li+ transference number of 0.67. The assembled Li||NCM811 cell demonstrates excellent rate performance, with a discharging capacity of 112.3 mAh g⁻¹ at 10C, and capacity retention of 87.6% after 260 cycles at 1C. Furthermore, the assembled graphite||NCM811 cell demonstrates excellent long‐term cycling stability with impressive capacity retention of 73.2% after 300 cycles 3C (1.8 mA cm−2). This work presents a promising approach to enhancing the cycling stability of GPEs for high‐voltage LIBs at high current density. [ABSTRACT FROM AUTHOR]

In this work, we present our improved protocols for the single batch syntheses of approximately 32 g of [NHMe3][CB11H12] and 10 g of Na[CHB11F11] as well as salt metathesis reactions, granting access to useful starting materials to introduce the [CHB11F11]− anion. This includes the trityl cation [Ph3C]+ and the bis‐1,2‐difluorobenzene‐silver(I)‐complex [Ag(odfb)2]+, as well as some applications of the shown compounds. The described methodology allows the synthesis of large amounts of both the [CB11H12]− and the [CHB11F11]− anion and therefore making them accessible for further reactions. To facilitate the reproducibility, we present video tutorials of the synthetic steps towards Na[CHB11F11]. [ABSTRACT FROM AUTHOR]

This article is a continuation of our previous research on the catalytic capability of a chiral copper complex based on commercially available (S)-2-aminomethylpyrrolidine and 3,5-di-tert-butylsalicylaldehyde with various counter-anions in the asymmetric Henry reaction. Our findings indicate that depending on the type of base used, chiral nitroalcohols with yields up to 98% and ee values up to 77%, as well as β-nitrostyrenes with yields up to 88%, can be produced. Additionally, it has been found that the outcome of the reaction and the catalytic properties of copper (II) complexes (S)-Cu1 and (S)-Cu2 are influenced by the structure of the aldehyde used. [ABSTRACT FROM AUTHOR]

The novel bioactive polysaccharide, Sacha inchi shell polysaccharide‐3 (SISP‐3), was isolated from the Sacha inchi (Plukenetia volubilis L.) shell using anion exchange and gel filtration chromatography. This neutral polysaccharide fraction, characterized by a triple‐helix structure and a molecular weight of 17,684 Da, was successfully isolated. The composition analysis of SISP‐3 revealed the presence of Rha, Ara, Gal, Glc, and Fru in molar ratios of 7.2%:41.7%:40.3%:4.1%:6.7%. The dominant glycosidic linkage in SISP‐3 was identified as ⟶4)‐Galp‐(1⟶, accompanied by a complex branching pattern. The results from RAW264.7 cell experiments showed that SISP‐3 significantly enhanced cell viability, phagocytosis, and NO production. Additionally, it significantly stimulated the production of cytokines, including TNF‐α, IL‐1β, and IL‐6, in RAW264.7 cells. These findings suggest that SISP‐3 serves as an immune active agent with immunomodulatory properties, indicating its potential as a natural immunomodulatory agent for various applications. [ABSTRACT FROM AUTHOR]

Anion defect engineering is proven to be an efficient approach to reconstruct the electronic configuration of carbon‐based magnetoelectric materials for targeted modulation of electromagnetic (EM) performance. However, traditional mono‐anionic doping suffers from low defect concentration and lacks diverse polarization mechanisms. In this work, multi‐anions (N/S/F) stepwise‐doped carbon/Fe3C magnetoelectric composites are elaborately constructed, wherein the predesigned N defects serve as activated sites for anomalously adopting S anions (Step I) and subsequent F anions (Step II) in non‐marginal areas of the carbon layer. It is found that S prefers to replace pyrrolic N defects while F tends to form dangling bonds with the C site adjacent to the pyridinic N. Intriguingly, besides the inherent polarized resonance of N defect at ≈15 GHz, customized S and F defects induce new polarization resonances at ≈10 GHz and ≈15+ GHz, respectively. Under a typical multi‐polarization effect with the synergetic magnetic response, the carbon/Fe3C composites with N/S/F defects harvest the broadest bandwidth of 8.28 GHz (9.72–18 GHz) at 2.55 mm, covering a wide frequency range almost from X to Ku bands. This work demonstrates the positive impact of localized multi‐defects customization and multi‐polarization effect on expanding microwave absorption bandwidth, providing valuable insights for the advanced design of ultra‐broadband absorbers. [ABSTRACT FROM AUTHOR]

Macrocyclic receptors have emerged as versatile and efficient molecular tools for the recognition and sensing of anions, playing a pivotal role in molecular recognition and supramolecular chemistry. The following review provides an overview of the recent advances in the design, synthesis, and applications of macrocyclic receptors specifically tailored for anion recognition. The unique structural features of macrocycles, such as their well-defined structures and pre-organised binding sites, contribute to their exceptional anion-binding capabilities that have led to their application across a broad range of the chemical and biological sciences. [ABSTRACT FROM AUTHOR]

Zinc–bromine flow batteries (ZBFBs) have received widespread attention as a transformative energy storage technology with a high theoretical energy density (430 Wh kg−1). However, its efficiency and stability have been long threatened as the positive active species of polybromide anions (Br2n+1−) are subject to severe crossover across the membrane at a high concentration. Herein, a novel highly hydrophilic complexing agent, N‐methyl‐N, N‐bis(2‐hydroxyethyl)‐1‐propanaminium bromide (PMDA), is developed to effectively manage bromine in a homogeneous posolyte, which realizes a low bromine crossover at a high operating concentration in ZBFBs. Both theoretical and experimental results suggest that the PMDA interacts with Br2n+1− and forms a larger‐size complex PMDABr2n+1. When adding 0.40 m PMDA, the bromine stays homogeneous at a high concentration up to 1.20 m, and its permeability is remarkably decreased by 74%. For demonstration, the ZBFB achieves a operating capacity record of 57.2 Ah L−1 in a homogeneous bromine posolyte with a high Coulombic efficiency of ≈90.0% and superior cycling stability (capacity retention rate of 100.0% per cycle). This work provides one innovative bromine management strategy to realize a high capacity and superior stability in ZBFBs. [ABSTRACT FROM AUTHOR]

We analyze the count rates of 40–139 keV ions that were measured in situ by the Low Energy Charged Particle instrument on Voyager 1 in order to identify the suprathermal ion anisotropies beyond the termination shock and in the very local interstellar (IS) medium (VLISM). The analysis results in a region of ∼9–10 au before the heliopause (HP) where the radial anisotropy of ions is negative, while the azimuthal ion anisotropy inside the heliosheath lies in the − T direction. In agreement to our previous analyses, we identify a positive radial anisotropy of ions up to at least ∼30 au beyond the HP, which becomes nearly zero from 2021 up to 2023 November (for ∼10 au). Notably, the anisotropy in the azimuthal direction is statistically zero throughout the upstream region, i.e., for ∼40 au past the HP, showing that the 40–139 keV ion anisotropy in the VLISM is only in the radial direction and has no azimuthal component. The presence of suprathermal ions of solar origin over such long spatial scales in the VLISM, along with the inflow of ions from IS space into the heliosheath, are important constraints for characterizing the interaction of the heliosheath with the VLISM. Our observations provide indications that V1 has entered a new regime in the VLISM since (at least) the year 2021, progressively developing characteristics akin to the pristine IS medium. Alternatively, this drop to nearly zero radial anisotropies beyond 2021 could be a manifestation of a prolonged compression/shock of solar origin. [ABSTRACT FROM AUTHOR]

In this paper, we report the unusual aggregation behavior of an important cyanine dye 1,1′-diethyl-4,4′-carbocynine iodide (DECI), also known as kryptocyanine, which interestingly depends on the type of the ionic liquid (IL) present in the aqueous solutions of the dye. Notably, the presence of a small amount of ILs containing [BF4]−, [PF6]− and [OTf]− anions induced the process of J-aggregation instantly, and the added ILs acted as promoters for J-aggregation, followed by time-dependent precipitation. In contrast to the above-mentioned ILs, the presence of a small amount of ILs containing Tf2N− anions induced the process of J- and H-aggregation simultaneously, followed by time-dependent conversion of H-aggregates to J-aggregates. Furthermore, the aggregation behavior of the dye was also found to be dependent on the concentration of the dye, temperature conditions, and nature of solubilizing media (polarity of the solvent and pH). [ABSTRACT FROM AUTHOR]

Groundwater from alluvial fan plains is the prevailing water source, especially for arid/semiarid regions, but its contamination poses substantial risks to water supply and public health. The recent study aims to assess the hydro-geochemistry, distribution, and potential health risks of NO3−, NO2−, and F− concentrations in the groundwater of previously unexplored health facilities in District Vehari, Punjab, Pakistan. In total, 75 groundwater samples were evaluated for NO3−, NO2−, and F− levels as well as pH, EC, TDS, CO32−, HCO3−, Cl−, Na+, Fe, K+, Ca2+, Mg2+, taste, odor, color, and turbidity. The Durav graph shows that the water type is Na-HCO3-Ca, with Na and HCO3 dominant, weak acids > strong acids, and alkaline ions > alkalis. Results revealed that drinking water samples (21.73% and 20%) taken from Tehsil Mailsi, and the Basic Health Unit (BHU) exceeded the WHO standard (1.5 mg/L) for F− concentration, respectively. Moreover, the mean chronic daily intake (CDI) of F− was 0.044, 0.018, and 0.02 mg/kg/day in children, men, and women, respectively. Similarly, the average CDI of NO3− was 0.113, 0.046, and 0.050 in children, men, and women, respectively, and the respective values of NO2− were 0.004, 0.001, and 0.001. The NO2− shows a significant range of hazard quotient (HQ) (0.0–1.172) in children. The range of HQ for F− was 0.0–3.114, 0.0–1.290, and 0.0–1.389 in children, men, and women, respectively. Additionally, the health risks analysis revealed an HQ > 1.0 for children in groundwater, indicating a potential carcinogenic risk from the F−. Pearson correlation and PCA analysis found a significant positive correlation (0.8) between NO3− and NO2− and a negative correlation (0.3) between F− and HCO3−. These findings highlight the need for groundwater treatment in healthcare facilities prior to water consumption. Enforcing international and national drinking water standards in healthcare units is vital to strengthening services and providing equitable access to safe drinking water. Legislative and efficient water management measures must be taken for the protection of public health. [ABSTRACT FROM AUTHOR]

The voltage-dependent anion channel 1 (VDAC1) is a crucial gatekeeper in the outer mitochondrial membrane, controlling metabolic and energy homeostasis. The available methodological approaches fell short of accurate visualization of VDAC1 in living cells. To permit precise VDAC1 imaging, we utilized the tetracysteine (TC)-tag and visualized VDAC1 dynamics in living cells. TC-tagged VDAC1 had a cluster-like distribution on mitochondria. The labeling of TC-tagged VDAC1 was validated with immunofluorescence. The majority of VDAC1-TC-clusters were localized at endoplasmic reticulum (ER)-mitochondria contact sites. Notably, VDAC1 colocalized with BCL-2 Antagonist/Killer (BAK)-clusters upon apoptotic stimulation. Using this new tool, we were able to observe VDAC1-TC at mitochondrial fission sites. These findings highlight the suitability of the TC-tag for live-cell imaging of VDAC1, shedding light on the roles of VDAC1 in cellular processes. [ABSTRACT FROM AUTHOR]

Anion sensing plays a crucial role in areas ranging from medical diagnostics to environmental monitoring. Dipyrromethane‐based compounds offer a versatile platform for developing colorimetric and fluorescent chemosensors, owing to their structural tunability and favorable optical properties. This review provides a concise overview of current advancements in anion sensing using dipyrromethane molecular framework. We examined the diverse strategies employed in designing dipyrromethane‐based anion sensors. Emphasis is placed on the structure‐function relationships that dictate anion affinity and selectivity. Key sensing mechanisms, including visual detection, UV‐vis studies, NMR studies, and fluorescence modulation, are explored. Finally, the synthetic routes for the synthesis of chemosensors are mentioned in detail. Given the efficiency and flexibility of dipyrromethane‐based sensor, we believe that major developments are to be expected in the field of both sensor and analytical chemistry. [ABSTRACT FROM AUTHOR]

Tetrahydro-4H-thiopyran-4-one 1-oxide 1 and sulfinyl-di-tert-butylpropionate 2 were reported as sources of bis-sulfenate anion and applied in a double pallado-catalyzed cross-coupling reaction for the synthesis of symmetrical biarylsulfoxides, tolerating a large array of electronic properties and bulkiness. The photophysical properties of a biarylsulfoxide have been explored, demonstrating an unreported TADF phenomenon on sulfoxide-containing scaffolds. [ABSTRACT FROM AUTHOR]

The synthesis of potassio-1H-silolides and -germolides substituted with an amidinate-stabilized silylene is reported. Both anions undergo a thermal rearrangement to the 2H-isomer yielding cyclic sila- and germavinyl anions. The reaction is driven by complex formation with metal ions. [ABSTRACT FROM AUTHOR]

Zn metal as a promising anode for aqueous batteries suffers from severe zinc dendrites, anion‐related side reactions, hydrogen evolution reaction (HER) and narrow electrochemical stable window (ESW). Herein, an "anions‐in‐colloid" hydrated deep eutectic electrolyte consisting of Zn(ClO4)2 ⋅ 6H2O, β‐cyclodextrin (β‐CD), and H2O with mass ratio of 7 : 4.5 : 3 (ACDE‐3) is designed to improve the stability of zinc anode. The ACDE‐3 reconfigures the hydrogen‐bond (HB) network and regulates the solvation shell. More importantly, the hydroxyl‐rich β‐cyclodextrins (β‐CDs) in ACDE‐3 self‐assemble into micelles, in which the steric effect between adjacent β‐CDs in micelles restricts the movement of anions. This unique "anions‐in‐colloid" structure enables the eutectic system with a high Zn2+ transference number (tZn2+) of 0.84. Thus, ACDE‐3 inhibits the formation of dendrite, prevents the anion‐involved side reactions, suppresses the HER, and enlarges the ESW to 2.32 V. The Zn//Zn symmetric cell delivers a long lifespan of 900 hours at 0.5 mA cm−2, and the Zn//Cu half cells have a high average columbic efficiency (ACE) of 97.9 % at 0.5 mA cm−2 from cycle 15 to 200 with a uniform and compact zinc deposition. When matched with a poly(1,5‐naphthalenediamine) (poly(1, 5‐NAPD)) cathode, the full battery with a low negative/positive capacity (N/P) ratio of 2 can still cycle steadily for 200 cycles at a current density of 1.0 A g−1. Additionally, this electrolyte has been proven to be operative over a wide temperature range from −40 °C to 40 °C. [ABSTRACT FROM AUTHOR]

Herein, we present a density functional theory with dispersion correction (DFT‐D) calculations that focus on the intercalation of ionic liquids (ILs) electrolytes into the two‐dimensional (2D) Ti3C2Tx MXenes. These ILs include the cation 1‐ethyl‐3‐methylimidazolium (Emim+), accompanied by three distinct anions: bis(trifluoromethylsulfonyl)imide (TFSA−), (fluorosulfonyl)imide (FSA−) and fluorosulfonyl(trifluoromethanesulfonyl)imide (FTFSA−). By altering the surface termination elements, we explore the intricate geometries of IL intercalation in neutral, negative, and positive pore systems. Accurate estimation of charge transfer is achieved through five population analysis models, such as Hirshfeld, Hirshfeld‐I, DDEC6 (density derived electrostatic and chemical), Bader, and VDD (voronoi deformation density) charges. In this work, we recommend the DDEC6 and Hirshfeld‐I charge models, as they offer moderate values and exhibit reasonable trends. The investigation, aimed at visualizing non‐covalent interactions, elucidates the role of cation‐MXene and anion‐MXene interactions in governing the intercalation phenomenon of ionic liquids within MXenes. The magnitude of this role depends on two factors: the specific arrangement of the cation, and the nature of the anionic species involved in the process. [ABSTRACT FROM AUTHOR]

Studying the regulatory mechanisms in different tissues of pepper is crucial for understanding organ formation, growth, and development. However, relevant studies are far from sufficient. In the current study, the stipe, calyx, pericarp, placenta, and seed of ripe pepper were sampled, and metabolites were determined by the untargeted metabolomics method. Transcriptome sequencing was performed by Illumina NovaSeq 6000, and then a high-throughput data set was built. The results showed that a total of 4879 annotated metabolites were detected in 15 samples of the five tissues under positive and negative ion mode. A total of 110.66 Gb of clean data was obtained by transcriptome sequencing, the clean data of each sample reached 6.21 Gb, and a total of 35 336 annotated expression genes were obtained. Furthermore, validate the accuracy of the data by combining principal component analysis and other methods. In summary, this study provides valuable information for the genetic improvement and breeding of peppers, and it holds potential application value, particularly in enhancing the quality and nutritional value of pepper fruits. [ABSTRACT FROM AUTHOR]

The document from Frontiers in Veterinary Science delves into TMR ingredients, experimental cow grouping, elution procedures, primer sequences, and metabolite analysis in dairy cows. It provides detailed data on nutrient levels, milk production, metabolites, and microbial communities in A1A1 and A2A2 cows, highlighting potential metabolic differences between the two groups. The document categorizes metabolites based on their regulation and provides insights into the impact of chemical compounds on biological processes, offering valuable information for researchers studying dairy cow nutrition, microbiota, and metabolomics. [Extracted from the article]

​​​​​​​Ocean CO2 uptake and acidification in response to human activities are driven primarily by the rise in atmospheric CO2 but are also modulated by climate change. Existing work suggests that this "climate effect" influences the uptake and storage of anthropogenic carbon and acidification via the global increase in ocean temperature, although some regional responses have been attributed to changes in circulation or biological activity. Here, we investigate spatial patterns in the climate effect on surface ocean acidification (and the closely related carbonate chemistry) in an Earth system model under a rapid CO2-increase scenario and identify a different driving process. We show that the amplification of the hydrological cycle, a robustly simulated feature of climate change, is largely responsible for the spatial patterns in this climate effect at the sea surface. This "hydrological effect" can be understood as a subset of the total climate effect, which includes warming, hydrological cycle amplification, circulation, and biological changes. We demonstrate that it acts through two primary mechanisms: (i) directly diluting or concentrating dissolved ions by adding or removing freshwater and (ii) altering the sea surface temperature, which influences the solubility of dissolved inorganic carbon (DIC) and acidity of seawater. The hydrological effect opposes acidification in salinifying regions, most notably the subtropical Atlantic, and enhances acidification in freshening regions such as the western Pacific. Its single strongest effect is to dilute the negative ions that buffer the dissolution of CO2, quantified as alkalinity. The local changes in alkalinity, DIC, and pH linked to the pattern of hydrological cycle amplification are as strong as the (largely uniform) changes due to warming, explaining the weak increase in pH and DIC seen in the climate effect in the subtropical Atlantic Ocean. [ABSTRACT FROM AUTHOR]

Solid‐electrolyte interphase (SEI) plays a decisive role in building reliable Li metal batteries. However, the scarcity of anions in Helmholtz layer (HL) caused by electrostatic repulsion usually leads to the inferior SEI derived from solvents, resulting in dendrites and ‘dead’ Li. Therefore, regulating the distribution of anions in electric double layer (EDL) and continuously introducing more anions into HL to tailor anions‐derived SEI is crucial for achieving stable Li plating/stripping. Herein, by jointly utilizing the controlled defects of reduced graphene oxide (rGO) and the oriented dipoles of ferroelectric BaTiO3 (BTO), the rGO‐BTO composite layer sustainedly brings more TFSI− and NO3− into anion‐defecient HL, promoting favorable decomposition of anions and guiding the generation of robust and fast‐Li+‐transport SEI containing more inorganics LiF and Li3N species. Thus, the resulting Li deposit shows smooth and dense morphologies without dendrites, leading to high average Coulombic efficiency. The Li//Cu@rGO‐BTO (10 mAh cm−2 plated Li) cell exhibits an enhanced Li plating/stripping stability (2700 h) and a higher rate capability. The LiFePO4 full cell (N/P≈6.3) using rGO‐BTO displays an enhanced capacity retention (82.0 % @ 430 cycles). This work provides a new insight on the construction of robust SEI by regulating the distribution of anions within EDL. [ABSTRACT FROM AUTHOR]

Male infertility is one of the most common reproductive dysfunctions. Despite oligospermia being a cause of infertility, few studies have been conducted on it. This study aimed to investigate differences in semen metabolic patterns in patients with oligospermia and to identify potential biomarkers associated with oligospermia. Semen samples from oligospermia patients (20 cases) and healthy controls (20 cases) were detected by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), and 72 and 89 metabolites were identified as potential markers in positive and negative ion modes, respectively. In addition, the results identified multiple metabolic pathways in patients with oligospermia, such as glycine serine and threonine metabolism, Synthesis and degradation of ketone bodies, Valine, leucine, and isoleucine degradation. These results described unique metabolic characteristics of semen in patients with oligospermia and provided novel insights into the mechanism of the semen disorder. [ABSTRACT FROM AUTHOR]

Background: Patients undergoing high-risk surgeries with acid-based disorders are associated with poor outcomes. The screening of mixed acid-based metabolic disorders by calculating delta anion gap (AG)/delta bicarbonate (Bic) has a clinically relevant role in patients with high AG metabolic acidosis (MA), however its utility in individuals facing high-risk surgical procedures remains unclear. Objective: Characterize metabolic acidosis using delta-AG/delta-Bic and its associations in patients undergoing high-risk surgeries with possible outcome-related complications. Design: Prospective observational multicentric study. Setting: Three tertiary hospitals in Brazil. Patients: Patients undergoing high-risk surgeries, aged 18 years or older, requiring postoperative critical care. Main outcome measures: Patients undergoing high-risk surgeries monitored during the postoperative phase across three distinct intensive care units (ICUs), with assessment encompassing laboratory analyses upon admission and 24 h thereafter. Patients with MA and with elevated AG within 24 h were separated into 3 subgroups: [G1 – delta-AG/delta-Bic < 1.0] MA associated with hyperchloremia; [G2 – delta-AG/delta-Bic between 1.0 and 1.6] MA and no mixed disorders; and [G3 – delta-AG/delta-Bic > 1.6] MA associated with alkalosis. Primary endpoint was 30-day mortality. The secondary endpoints were cardiovascular, respiratory, renal, neurological, coagulation and infective complications. Results: From the 621 surgical patients admitted to ICU, 421 (51.7%) had any type of acidosis. After 24 h, 140 patients remained with MA with elevated AG (G1: 101, G2: 18, and G3: 21). When compared to patients from subgroups 1 and 3, the subgroup with no mixed disorders 2 showed higher 30-day mortality (adjusted HR = 3.72; 95% CI 1.11–12.89, p = 0.001), cardiovascular complications (p = 0.001), ICU mortality (p = 0.03) and sum of all complications during the ICU period (p = 0.021). Conclusion: In the postoperative time, patients with metabolic acidosis and no mixed disorders present higher ICU-Mortality and higher cardiovascular postoperative complications when compared with patients with combined hyperchloremia or alkalosis. Delta-AG/delta-Bic can be a useful tool to evaluate major clinical outcomes in this population. Key points: In the context of high-risk surgeries, patients experiencing metabolic acidosis accompanied by an elevated anion gap exhibit a reduced likelihood of survival in the intensive care unit (ICU). The application of the delta-AG/delta-Bic ratio for assessing mixed disorders in patients with elevated anion gap acidosis during the early postoperative phase proves to be a valuable and clinically relevant tool. A subgroup of patients presenting metabolic acidosis accompanied by an elevated anion gap although without associated disorders, demonstrate a poorer clinical prognosis within the ICU setting. [ABSTRACT FROM AUTHOR]

Comprehensive Summary Two families of cyclopentadienyl (Cp)/carboranyl heteroleptic sandwiched organolanthanide complexes, namely [Ln{η5:σ‐Me2C(C5H4)(C2B10H10)}2][Li(DME)3] (1Ln, Ln = Tb, Dy, Ho, Er) and [2‐THF‐2'‐(μ2‐Cl)Li(THF)3‐2,2'‐Ln(nido‐1,7‐C2B9H11)Cp*] (2Dy), were synthesized. Family of 1Ln has been proposed based on the mixing‐ligands idea by linking Cp and nido‐dicarborllide. However, the carborane cage of [Me2C(C5H4)(C2B10H10)]2− deprotons and forms a mono‐C− anion rather than deboron to form dicarborllide dianion. Hence, the family of 1Ln features a dysprosocenium skeleton with extra two coordination of C− anions of carborllides. Such coordination geometry is more like a tetrahedron if abstracting the centroids of two coordinated Cp rings. In this cubic‐type geometry, no significant magnetic axiality is presented; only 1Dy and 1Tb show field‐induced slow magnetic relaxation behavior below 10 K. Inspired by 1Ln, the free pentamethylcyclopentadienyl (Cp*−) and nido‐dicarborllide ligands are used to sandwich central Dy3+ ion, achieving heteroleptic complex 2Dy. The bending angle by linking the centroid of Cp*−, Dy3+ and C2B32− in 2Dy is increased to 132.8(1)°. As such, the effective energy barrier for magnetic reversal (Ueff) and magnetic blocking temperature TB (ZFC) are both increased (Ueff = 616(10) K; TB = 6 K). The effort of further enhancing Ueff and TB in such heteroleptic organolanthanide sandwiches should rely on keeping increasing the ligand axiality. [ABSTRACT FROM AUTHOR]

ABSTRACT A practical and straightforward strategy for the synthesis of ferrocene appended furopyranone, furochromenone, and benzofuranone via a metal‐free annulation reaction of imidazolium ylide with enone mediated by saccharin‐based ionic liquid has been reported. The mechanistic studies show an approach through synergistic dual activation of enone and imidazolium ylide via cation and anion of ionic liquid, respectively. This operationally simple protocol offers an easy and rapid access to a library of ferrocene appended furopyranone, furochromenone, and benzofuranone in moderate to good yields through the involvement of a six‐membered transition state. [ABSTRACT FROM AUTHOR]

Two complexes {[GdCu5(GlyHA)5(H2O)7Cr(C2O4)3]·11.02H2O}n (1) and {{[GdCu5(GlyHA)5(H2O)6]μ2-[Cu(C2O4)2(H2O)]}2μ4-[Cu(C2O4)2]·15.8H2O}n (2), were obtained as outcomes of the reactions between the cationic hexanuclear {GdCu5(GlyHA)5}3+ 15-metallacrown-5 complex (where GlyHA2− = glycinehydroxamate) and the anionic oxalate complexes K3[Cr(C2O4)3] or K2[Cu(C2O4)2]. Both 1 and 2 possess polymeric 1D-chain structures according to X-ray structural analysis. As a consequence of the geometric orientations of the donor atoms in the oxalates from [Cr(C2O4)3]3−, the Cu5 mean planes of neighboring 15-metallacrown-5 units {GdCu5(GlyHA)5}3+ are angled at 75.5° to each other, which leads to formation of a zig-zag motif in the 1D-chains of complex 1. The centrosymmetric complex 2 contains two structurally different bis(oxalato)cuprate anions μ2-[Cu(C2O4)2(H2O)]2−, for one of which, coordination to two adjacent {GdCu5(GlyHA)5}3+ units leads to formation of linear 1D-chains in 2, while the second type, μ4-[Cu(C2O4)2]2−, is coordinated to four {GdCu5(GlyHA)5}3+ units, causing the cross-linking of single 1D-chains into a double-chain 1D coordination polymer. Studies of χMT vs. T data for 1 and 2 in a 2–300 K temperature range revealed the presence of both ferromagnetic and antiferromagnetic interactions amongst paramagnetic centres. The experimental χMT vs. T data for 1 were fitted using a model which takes into account exchange interactions between adjacent copper(II) ions, the Gd–Cu exchange interactions within {GdCu5(GlyHA)5}3+ units and additionally Gd–Cr exchange interactions. Fitting of the χMT vs. T data for 2 was not possible, since coordination of μ4-[Cu(C2O4)2]2− to {GdCu5(GlyHA)5}3+ led to the non-equivalence of several Cu–Cu exchange interactions within the metallacrown units and hence a superfluity of fittable parameters. Complexes 1 and 2 are the first examples of 15-metallacrown-5 complexes demonstrating a magnetocaloric effect (−ΔSM at 13 T reaches 24.26 J K−1 kg−1 at 5 K and 19.14 J K−1 kg−1 at 4 K for 1 and 2, respectively). [ABSTRACT FROM AUTHOR]

Copper sulfides exhibit various significant physical properties and have wide potential applications. In order to synthesize copper sulfides and investigate the anion substitution possibility of Cu3P, we immersed Cu3P in sodium sulfide solution. From X‐ray diffraction spectra results, copper sulfides, namely Cu2S and Cu7.2S4, were observed, indicating that anion substitution between S2− and P3− ions did occur. Consequently, we investigated the resistive switching (RS) properties of these two phases in the presence of Cu3P. We found that the Cu2S‐Cu3P composite exhibited a high Off/On ratio (88) and a long retention time (>103 s). However, the Cu7.2S4‐Cu3P composite exhibited no RS performance. In addition, we discussed the conduction and resistive switching mechanisms. Our work enriches the preparation method of copper sulfides and provides a reference for enhancing RS performance. [ABSTRACT FROM AUTHOR]