Ionic Metal Research Articles

Design Rule Hidden from The Eye in S/N‐Bridged Ancillary Ligands for Copper(I) Complexes Applied to Light‐Emitting Electrochemical Cells

AbstractEnhancing low‐energy emitting Cu(I)‐ionic transition metal complexes (iTMCs) light‐emitting electrochemical cells (LECs) is of utmost importance towards Cu(I)‐iTMC‐based white‐emitting LECs. Here, the ancillary ligand design includes (i) extension of π‐systems and (ii) insertion of S‐bridge between heteroaromatics rings. This led to two novel heteroleptic Cu(I)‐iTMCs: 2‐(pyridin‐2‐yl‐l2‐azanyl)quinoline (CuN2) and 2‐(naphthalen‐2‐ylthio)quinoline (CuS2) as N^N and bis[(2‐diphenylphosphino)phenyl] ether as P^P, exhibiting improved photoluminescence quantum yields (ϕ) and thermally activated delayed fluorescence processes compared to their reference Cu(I)‐iTMCs: di(pyridin‐2‐yl)‐l2‐azane (CuN1) and di(pyridin‐2‐yl)sulfane (CuS1). Despite CuS2 stands out with the highest ϕ (38% vs 17 / 14 / 1% for CuN1 / CuN2 / CuS1), only CuN2‐LECs show the expected enhanced performance (0.35 cd A−1 at luminance of 117 cd m−2) compared to CuN1‐LECs (0.02 cd A−1 at6 cd m−2), while CuS2‐LECs feature low performances (0.04 cd A−1 at 10 cd m−2). This suggests that conventional chemical design rules are not effective towards enhancing device performance. Herein, nonconventional multivariate statistical analysis and electrochemical impedance spectroscopy studies allow to rationalize the mismatch between chemical design and device performance bringing to light a hidden design rule: polarizability of the ancillary ligand is key for an efficient Cu(I)‐iTMC‐LECs. All‐in‐all, this study provides fresh insights for the design of Cu‐iTMCs fueling research on sustainable ion‐based lighting sources.

Preparation and characterization of ionic metal-based anticancer formulations of the type [bis-DACH tolfenamate metal {Co(II), Cu(II) and Zn(II)}] complexes: Binding studies with ct-DNA/tRNA, cleavage and cytotoxic activity against chemoresistant cancer cells

A series of ionic metallo-NSAID’s having the formulae [Co(DACH)2(H2O)2](tolf)21, [Cu(DACH)2(H2O)2](tolf)22 and [Zn(DACH)2(H2O)2](tolf)23 where DACH and tolf− are 1,2-diaminocyclohexane and tolfenamate anion, respectively were synthesized. Complexes 1–3 were characterized by FT–IR, EPR, 1H/13C NMR, UV–vis and ESI–MS spectrometry methods. The bonding features as well as the electronic structure of all the complexes were optimized using DFT studies. Binding affinity of parent NSAID and 1–3 complexes with ct–DNA/tRNA were studied by using various complementary biophysical methods. The corroborative results of these experimental studies revealed that they were capable to interact with the therapeutic targets, ct–DNA/tRNA by the electrostatic interactions, showing higher preference for tRNA as compared to ct–DNA as quantified by their binding strength (Kb and Ksv values). It was also observed that the complexes exhibited much higher binding affinity than the parent free NSAID. A concentration-dependent cleavage of the complexes was observed with tRNA which promoted the hydrolysis of RNA. The cytotoxicity of 1–3 was evaluated against chemo-resistant phenotypes of cancers, viz., breast cancer cell line (MCF- 7), cervical cancer cell line (SiHa), triple-negative breast cancer cell (MDA-MB-231), oral squamous cancer cell (AW13516) and lung cancer cell line (Hop-62) by SRB assay. The cytotoxicity activity results displayed that among all the ionic tolfenamate metal complexes, complex 2 showed a much superior cytotoxic profile against treated cancer cell lines (SiHa, MDA-MB-231, AW13516, MCF-7 and Hop-62) with a good GI50 value of (4.7 ± 0.03) µg/ml, (10.5 ± 0.36) µg/ml, (19.2 ± 0.02) µg/ml, (4.1 ± 0.05) µg/ml, and (18.2 ± 0.04) µg/ml, respectively, while the complexes 1 and 3 showed moderate activity. Cell morphology studies were carried out in AW13516, MDA–MB–231, MCF–7 and Hop–62 cells with the incubation of complexes for a period of 48 h which implicated that the cells exposed to complex 2 presented round features and were nonadherent in culture. These morphological changes indicated that complex 2 was capable of inducing cell death, probably by apoptosis suggesting copper complex 2 was promising potent anticancer agent.

Phase Separation and Ion Diffusion in Ionic Liquid, Organic Solvent, and Lithium Salt Electrolyte Mixtures.

The highly desirable characteristics of ternary mixtures of ionic liquids, organic solvents, and metal salts make them a promising candidate for use in various electrothermal energy storage and conversion systems. In this study, using large-scale classical molecular dynamics simulations, we looked into 10 different ternary electrolyte mixtures using combinations of [EMIM]+, [BMIM]+, and [OMIM]+ cations with [NO3]-, [BF4]-, [PF6]-, [ClO4]-, [TFO]-, and [NTf2]- anions, tetraglyme, and Li salt to study the effect of ionic liquid composition on the phase behavior of ternary electrolyte mixtures. We uncovered that in these electrolytes, phase separation is mainly a function of pairwise binding energy of the constituents of the mixture. To corroborate this theory, several simulations are performed at various temperatures ranging from 260 to 500 K for each mixture, followed by calculating the binding energy of ionic liquid pairs using density functional theory. Our results verify that the transition temperature for the phase separation of each system is indeed a function of the pairwise binding energy of its ionic liquid pairs. It is also found that in some cases, the diffusion coefficient of the Li+ ions decreased even with the increase in the temperature, an effect that is attributed to the presence of condensed ionic domains in the electrolyte. This study provides a new insight for the design of multicomponent electrolyte mixtures for a wide range of energy applications.

Amino Acid-Derived Ionic Chiral Catalysts Enable Desymmetrizing Cross-Coupling to Remote Acyclic Quaternary Stereocenters.

Synthetic application of asymmetric catalysis relies on strategic alignment of bond construction to creation of chirality of a target molecule. Remote desymmetrization offers distinctive advantages of spatial decoupling of catalytic transformation and generation of a stereogenic element. However, such spatial separation presents substantial difficulties for the chiral catalyst to discriminate distant enantiotopic sites through a reaction three or more bonds away from a prochirality center. Here, we report a strategy that establishes acyclic quaternary carbon stereocenters through cross-coupling reactions at distal positions of aryl substituents. The new class of amino acid-derived ionic chiral catalysts enables desymmetrizing (enantiotopic-group-selective) Suzuki-Miyaura reaction, Sonogashira reaction, and Buchwald-Hartwig amination between diverse diarylmethane scaffolds and aryl, alkynyl, and amino coupling partners, providing rapid access to enantioenriched molecules that project substituents to widely spaced positions in the three-dimensional space. Experimental and computational investigations reveal electrostatic steering of substrates by the C-terminus of chiral ligands through ionic interactions. Cooperative ion-dipole interactions between the catalyst's amide group and potassium cation aid in the preorganization that transmits asymmetry to the product. This study demonstrates that it is practical to achieve precise long-range stereocontrol through engineering the spatial arrangements of the ionic catalysts' substrate-recognizing groups and metal centers.

In-situ construction of ionic ultramicroporous metal–organic frameworks for high-efficiency CO2/CH4 separation

The high-efficiency capture of CO2 from biogas by adsorption is highly desirable, which, yet faces the challenges regards of the unsatisfactory adsorption efficiency, selectivity, and regeneration performance. Herein, ionic ultramicroporous metal organic frameworks (IUM-MOFs) with high CO2 affinity are constructed by one-step in-situ coordination strategy and used for CO2/CH4 separation. The phenoxylate anion-functionalized ionic liquid (FIL) serves as competitive ligands in the formation of IUM-MOFs. The oxyl group exhibits high affinity with CO2 as the Lewis basic center, while the rigid counterion occupies the adsorption space of CH4 in the cavities of IUM-MOFs, thus bringing about superior CO2 adsorption capacity of 149 cm3 g−1 (150% higher than that of Cu-BTC) and high IAST predicted selectivity with CH4 of 22 under atmospheric condition. Mechanism analysis demonstrated that the formation of hydrogen bonds between CO2 with coordinated IL and H2O and IL-enhanced polarity of MOFs benefit to the CO2 adsorption. In addition, the IUM-MOFs could be facilely regenerated at 120 °C with favorable recycling stability. This work provides facile strategy for the rational design of IUM-MOFs and lays useful insights for structural tuning to promote their applications.

MIL-101(Cr) loaded simple ILs for efficient ammonia capture and selective separation

Capture and recovery of ammonia (NH3) from industrial exhaust is a win–win strategy for resource utilization and contaminants control. [CAM][Cl]@MIL-101(Cr) composite designed and prepared based on ionic liquids (ILs, carbamide chloride: [CAM][Cl]) and metal–organic frameworks (MOFs, MIL-101(Cr)) has exhibited potentials for NH3 capture capacity (11.61 mmol/g) and NH3/CO2 separation (SNH3/CO2 = 3,266). The selectivity is 3.13 times as high as that of the parent MIL-101(Cr) and higher than the highest values in literature. Not only that, the breakthrough experiment of NH3/CO2 mixture further proves that high-purity NH3 can be obtained in one step (Separation Factor is about 1518). Such excellent performance originates from the synergistic effect of various types of interaction sites and adsorption spaces. The theoretical calculation reveals that the hydrogen bond (HB) interaction between ILs and NH3 plays a greatly significant role in enhancing NH3 adsorption and separation selectivity of NH3/CO2 for the composite. In addition, the composite exhibits good structural stability and regenerability. More importantly, the novel design-strategy can avoid the challenge for precise control of the microstructure and channel environment of adsorbents, which is beneficial to the development of novel materials.

Efficient removal of alkali and alkaline earth metals from biodiesel using Ion-exchange resin: Performance and mechanism

Raw materials, production process, and other factors cause several metal ions to exist in biodiesel. Furthermore, the existence of alkali and alkaline earth metals seriously affects the quality and performance of biodiesel. To improve fuel quality, a 732 ion-exchange resin was used to reduce the contents of alkali and alkaline earth metal ions in Jatropha biodiesel. The adsorption efficiency of the ion-exchange resin for alkali and alkaline earth metal ions in biodiesel was evaluated using ion chromatography, while the adsorption mechanism of ion change resin on alkali and alkaline earth metal ions in biodiesel was elucidated via FTIR and XPS. In addition, the effects of ion-exchange resin on several key physiochemical properties of biodiesel, including oxidation stability, corrosivity, heat value and kinematic viscosity, were also explored. The results showed that the total content of alkali and alkaline earth metal ions in biodiesel was reduced by 88.19%, and the K+, Na+, Mg2+, and Ca2+ contents were reduced to 0.11 mg/kg, 0.89 mg/kg, 0.53 mg/kg, and 0.78 mg/kg, respectively, after removing the ion-exchange resin. In the removal process, the hydroxyl group of sulfonic acid group on the ion-exchange resin is broken, and the substitution adsorption reaction between H+ and the alkali and alkaline earth metal ions in biodiesel is carried out. Moreover, the oxidation induction period of biodiesel was prolonged by 40.8% owing to the reduction in the content of alkali and alkaline earth metal ions, which significantly blocked the decomposition pathways of unstable oxidation intermediates in biodiesel. The degree of copper corrosion in biodiesel did not change significantly before and after ion-exchange resin adsorption during short-term corrosion (3 h); however, the copper corrosion grade decreased from 2c to 1b after ion-exchange resin adsorption during long term corrosion (240 h). Nevertheless, the heat value and kinematic viscosity of biodiesel were observed to be independent of the ionic metal content.

Regulating energy gap in Ir-based ionic complexes to generate near-infrared emissions: Application in solid-state light-emitting electrochemical cells

Solid-state light-emitting electrochemical cells (LECs) exhibit high potential for commercial electronics owing to their simple solution-processable device architectures, low-voltage operation, and compatibility with inert metal electrodes. However, the low device efficiency of most deep-red and near-infrared (NIR) LECs hinders their application (external quantum efficiency (EQE) < 1.00%). In this study, we demonstrate a simple method to tune the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of iridium-based ionic transition metal complexes (iTMCs) to generate NIR emissions. We investigate a series of cationic iridium complexes with small energy gaps, with 2,2′-bibenzo[d]thiazole fixed as N^N ligand moiety mainly controlling the LUMO energy level, changing a series of C^N ligands. All complexes exhibited deep red/NIR phosphorescence, and these combined devices provided emission peaks at 690–730 nm and were applied as components in LECs, exhibiting a maximum EQE of 1.78% in electroluminescence devices. Using a host–guest emission system with the iridium complex YIr as the host and complex TBBI as the guest, the highest EQE of LECs could be further enhanced to>2.34%, which is the highest value reported for NIR LECs.

Effect of Metal Ions and Suspended Particles on Streamer Propagation

Metal contamination in insulating oil is one of the main threats to the safe and reliable operation of oil-immersed equipment such as on-load tap changers. The mechanism analysis of metal ions’ influence on the discharge process of insulating oil is rarely involved in previous studies. Herein, the generation mechanism of metal ions and suspended particles is summarized first for subsequent modeling. Numerical models are constructed to simulate the streamer propagation in oil, considering the effect of two forms of metal contaminant. The dissociation source term of ionic compounds is introduced into the charge continuity equation to elucidate the impact of metal ions on streamer propagation. The results reveal that adding metal ions increases the overall speed of the streamer and decreases the maximum field intensity at the head of the steamer compared to pure oil conditions. Excessive ion concentration hinders the streamer’s development by creating the space charge shielding effect. Charge accumulation on the surface of suspended metal particles is the leading cause for the branching or turning of the streamer channel. The size, quantity of the metal particles, and the landing location will significantly affect the streamer propagation characteristics, e.g., the landing location on the surface of the metal particle will determine whether the subsequent branching streamer head can further develop. The results contribute to a better understanding of the influence of ionic and particulate metal contaminants on the microscopic discharge process in insulating oil.

The Effect of the Interface Layer on the Electronic Parameters of the Light Emitting Electrochemical Cell (LEC) Device Based on Iridium (III) Complex that Calculated by Different Methods

We report a calculation of the electronic parameters and some optical measurement results of a light-emitting electrochemical cell (LEC), one of the most basic forms of electroluminescent films by modifying 4-(4-methoxy-N-naphthalen-1-ylanilino) benzoic acid (MA) as hole injection layer doped with an emissive layer that is ionic transition metal complex (Ir[dF(CF3)ppy]2(dtbpy))PF6-(Ir-iTMC). The electronic parameters of LEC device were computed using three different methods; Cheung and Cheung’s, Conventional Schottky and Norde, to evaluate the ideality factor (n), the barrier height () and the series resistance (Rs) of the LEC device. The formation on indium tin oxide (ITO) substrate was analyzed by Atomic Force Microscopy (AFM). The HOMO-LUMO energy level and electronic charge distribution of the MA molecule were computed theoretically using Chemissian software. The MA’s HOMO-LUMO energy level is determined to be EHOMO = −5.27 eV and ELUMO = −1.40 eV. The ITO surface has been modified with the Self-Assembled Monolayers (SAM) technique as an interlayer to improve the surface working function by simplifying hole injection from the ITO anode to the Hole Transport Layer (HTL) in the LEC. The Ir- iTMC complexes containing Π-conjugated bridging ligand shown better external quantum efficiency (EQE), reaching to 1.49%. The max luminance values of the bare-LEC and LEC-MA are measured as 145 cd m−2 and 1240 cd m−2, respectively.

Kinetic analysis of an ionic liquid-based metal extraction process using a single droplet extraction column

In this study a liquid-liquid extraction (LLX) process has been investigated based on experimental analysis and kinetic modelling. The purpose of this investigation is (1) to understand the mass transfer behaviour, (2) to determine the rate limiting step via evaluating different mass transfer models, and (3) to estimate the mass transfer and kinetic parameters. This has been discussed in the context of the extraction of Co by the ionic liquid (IL) [P8888][Oleate] as an example of LLX with chemical reaction. Mass transfer models, with and without a chemical reaction, are evaluated based on a statistical cross-validation method. The following operational parameters are included in the analysis: column lengths, droplet diameter, droplet rising velocity and continuous and dispersed phase concentrations on Co uptake. This method reveals that a single parameter representing the external mass transfer resistance can describe the forward extraction of Co (i.e., into the IL) for the whole data set sufficiently accurate (error ±30%) regardless of the studied operational conditions. Back-extraction of Co from pre-loaded IL droplets shows a different transfer mechanism. Now the mass transfer in the dispersed IL phase dominates the process which is attributed to a change of the physical properties of the pre-loaded IL.

Confining organic cations in metal organic framework allows molecular level regulation of CO2 capture

AbstractHigh tunability of both ionic liquids (ILs) and metal organic frameworks (MOFs) enables great opportunity in the rational designation of IL/MOF composites for physical adsorption and separation. Traditionally, cations and anions of ILs as an entirety are combined with MOFs either inside or outside the microchannels. Herein, organic cations of ILs were confined into Cu‐BTC and the champion adsorbent is obtained by using 1‐propionic acid‐3‐vinylimidazole bromide as the precursor with a moderate loading amount, exhibiting higher CO2 uptakes of 8/5 mmol g−1 than Cu‐BTC (6.0/3.5 mmol g−1) at 273/298 K and 100 kPa, associating with significantly improved CO2/N2(CH4) selectivities. The organic cations are interacted with two adjacent CuII2(CRO2)2 paddle wheel units of Cu‐BTC, expanding the CuO bond to strengthen the CO2 affinity of open Cu sites and also serving as an additive CO2 adsorptive site. The promotion of CO2 capture ability is further reflected in the dynamic column breakthrough experiment.

Sonoluminescence of Aqueous Solutions of CaCl2 and NaCl: The Effect of Concentration

The structure of the sonoluminescence spectra of argon-saturated aqueous solutions of CaCl2 and NaCl of various concentrations is considered in detail. The frequency of ultrasound is 20 kHz, and the output power is 18 W. The spectrum of the CaCl2 solution changes considerably as the concentration rises. The intensity of the continuum passes through a maximum near the saturation concentration. Atomic, ionic, and molecular metal lines are observed for medium concentration values and disappear at high concentrations. Similar behavior is displayed by the spectra of NaCl solutions. The differences between the spectra are explained by the change in the vapor–gas content of the bubbles and the nature of their population, from large and non-inertial to small and pulsating inertially.

Excited State Engineering in Ag29 Nanocluster through Peripheral Modification with Silver(I) Complexes for Bright Near-Infrared Photoluminescence

The optical property of an ionic metal nanocluster (NC) is affected by the ionic interaction with counter ions. Here, we report that the modification of trianionic [Ag29(BDT)12(TPP)4]3- NC (BDT: 1.3-benzenedithiol; TPP: triphenylphosphine) with silver(I) complexes led to the intense photoluminescence (PL) in the near-infrared (NIR) region. The binding of silver(I) complexes to the peripheral region of Ag29 NC is confirmed by the single-crystal X-ray diffraction (SCXRD) measurement, which is further supported by electrospray ionization mass spectrometry (ESI-MS) and nuclear magnetic resonance (NMR) spectroscopy. The change of excited-state dynamics by the binding of silver(I) complexes is discussed based on the results of a transient absorption study as well as temperature-dependent PL spectra and PL lifetime measurements. The modification of Ag29 NCs with cationic silver(I) complexes is considered to give rise to a triplet excited state responsible for the intense NIR PL. These findings also afford important insights into the origin of the PL mechanism as well as the possible light-driven motion in Ag29-based NCs.

Structure Transformation and Morphologic Modulation of Supramolecular Frameworks for Nanoseparation and Enzyme Loading.

Supramolecular framework (SF) encourages the emergence of porous structures with molecular flexibility while the dimension and morphology controls are less involved even though critical factors are vital for various utilizations. Targeting this purpose, two isolated components are designed and their stepped combinations via ionic interaction, metal coordination, and hydrogen bond into framework assembly with two morphologic states are realized. The zinc coordination to an ionic complex of polyoxometalate with three cationic terpyridine ligands constructs 2D hexagonal SF structure. A further growth along perpendicular direction driven by hydrogen bonding between grafted mannose groups leads to 3D SF assemblies, providing a modulation superiority in one framework for multiple utilizations. The large area of multilayered SF sheet affords a filtration membrane for strict separation of nanoparticles/proteins under gently reduced pressures while the granular SF assembly demonstrates an efficient carrier to load and fix horse radish peroxidase with maintained activity for enzymatic catalysis.

Ionic liquid hybrid metal–organic frameworks for efficient adsorption and selective separation of ammonia at high temperature

Efficient adsorption and selective separation of ammonia at high temperature is a crucial and challenging issue. In this work, a series of stable ionic liquid hybrid materials have been developed by simple impregnation of ionic liquids into stable metal–organic framework Al-fum with 1D pores. The hybrid material [C2N][Zn3Cl7]@Al-fum-60% exhibited an exceptionally high uptake (9.9 mmol/g at 80 °C, 8.8 mmol/g at 100 °C) at high temperature, excellent uptake (9.8 mmol/g at 25.0 °C) at low ammonia concentration (100,000 ppm), and remarkable selective separation performance (selectivity factor is 25.1) of NH3 from NH3/CO2 mixture at high temperature. The NH3 uptake of [C2N][Zn3Cl7]@Al-fum-60% at 100 °C was higher than the capacity of most of typical porous NH3 adsorbents at room temperature. It is revealed that such superior NH3 capacity and selective separation performance are mainly attributed to coordination interactions of NH3 to Zn centre of the ionic liquids and the hydrogen bonding interactions of NH3 with Cl of the ionic liquids and NH3 with μ-OH of Al-fum.

Tracking soluble and nanoparticulated titanium released in vivo from metal dental implant debris using (single-particle)-ICP-MS

BackgroundThis work studies the presence of the Ti, Al and V metal ions and Ti nanoparticles released from the debris produced by the implantoplasty, a surgical procedure used in the clinic, in rat organs. MethodsThe sample preparation for total Ti determination was carefully optimized using microsampling inserts to minimize the dilution during the acid attack of the lyophilized tissues by a microwave-assisted acid digestion method. An enzymatic digestion method was optimized and applied to the different tissue samples in order to extract the titanium nanoparticles for the single-particle ICP-MS analysis. ResultsA statistically significant increase was found for Ti concentrations from control to experimental groups for several of the studied tissues, being and particularly significant in the case of brain and spleen. Al and V concentrations were detected in all tissues but they were not different when comparing control and experimental animals, except for V in brain. The possible presence of Ti-containing nanoparticles mobilized from the implantoplasty debris was tested using enzymatic digestions and SP-ICP-MS. The presence of Ti-containing nanoparticles was observed in all the analyzed tissues, however, differences on the Ti mass per particle were found between the blanks and the digested tissue and between control and experimental animals in some organs. ConclusionThe developed methodologies, both for ionic and nanoparticulated metal contents in rat organs, have shown the possible increase in the levels of Ti both as ions and nanoparticles in rats subjected to implantoplasty.

Influences of input concentration, media particle size, metal cation valence, and ionic concentration on the transport, long-term release, and particle breakage of polyvinyl chloride nanoplastics in saturated porous media

The environmental impact of nanoplastics has gradually attracted widespread attention; however, nanoplastics of polyvinyl chloride, one of the most commonly used plastics, have not yet been studied. In this study, we investigated the transport, long-term release behavior, and particle fracture of polyvinyl chloride nanoplastics (PVC NPs) in saturated quartz sand with different metal cations, ionic concentrations, input concentrations, and sand grain sizes by determining breakthrough, long-term release, and particle size distribution curves. The breakthrough curves and retention profiles were simulated by a mathematical model. The transport of PVC NPs increased with increased input concentration and sand grain size, which could be predicted by the Derjaguin–Landau–Verwey–Overbeek (DLVO) and colloid filtration theories. Increased ionic concentration and metal cation valence could restrain the transport of PVC NPs in saturated quartz sand owing to the decreased energy barrier between PVC NPs and sand grains. The total released amount of PVC NPs in the long-term release tests with different experimental conditions ranged from 3.91 to 21.95%. Increased sand grain size and decreased metal cation valence and ionic concentration resulted in an increased released amount of retained PVC NPs in saturated quartz sand, indicating increased release ability and mobility. The particle fracture results indicated that the PVC NPs were not broken down during long-term release under the experimental conditions of this research. This opens up a completely new and meaningful study of whether nanoplastics are broken down into smaller nanoplastics during their long-term release under various conditions.

Ionic liquid incorporated metal–organic framework as high conductivity solid conductor

As a new type of composite ionic conductor, the combination of ionic liquids (ILs) and metal organic framework (MOF) shows a good application prospect. In this study, two ionic liquids, 1,3-dimethylimidazolium tetrafluoroborate ([Dmim][BF4]) and 1-Allyl-3-methylimidazolium dicyanamide ([Amim][N(CN)2]) were successfully combined with MIL-101(Cr). The influence of the amount of ionic liquid and temperature on the electrical conductivity of composite IL@MIL-101(Cr) was explored. The optimal electrical conductivity reached 3.73 × 10-3S·cm−1 ([Dmim][BF4]) and 2.69 × 10-3S·cm−1 ([Amim][N(CN)2]) respectively when exposed to air at 100 °C. It is worth noting that the ionic conductivity of all composites exhibits linear Arrhenius behavior. Since the activation energies of composites are closely related to the type of ionic liquid and MOF types, these two composites exhibit different activation energies. The reason for the difference in activation energies is analyzed with the aid of quantum chemical calculations.

Flux Growth of an Intermetallic with Interstitial Fluorides via Decomposition of a Fluorocarbon.

La15(FeC6)4F2 was grown as large crystals by reacting iron in a La/Ni eutectic flux in the presence of decafluorobiphenyl (C12F10) which acts as both a carbon and fluoride source. This mild fluorinating technique enables the isolation of an intermetallic product containing fluoride interstitials, as opposed to forming ionic metal fluorides. The compound adopts a structure in the hexagonal crystal system with space group P6̅ which features FeC6 units composed of a central iron atom coordinated by three ethylenide units in a trigonal planar configuration. The structure is related to the previously reported La15(FeC6)4H, but with fluoride fully occupying the interstitial hydride positions, which induces partial occupancies and site splitting disorder in the adjacent layers of lanthanide ions. No supercell formation is observed.