Stable Conversion Chemistry‐Based Lithium Metal Batteries Enabled by Hierarchical Multifunctional Polymer Electrolytes with Near‐Single Ion Conduction

The low Coulombic efficiency and serious safety issues resulting from uncontrollable dendrite growth have severely impeded the practical applications of lithium (Li) metal anodes. Herein we report a stable quasi‐solid‐state Li metal battery by employing a hierarchical multifunctional polymer electrolyte (HMPE). This hybrid electrolyte was fabricated via in situ copolymerizing lithium 1‐[3‐(methacryloyloxy)propylsulfonyl]‐1‐(trifluoromethanesulfonyl)imide (LiMTFSI) and pentaerythritol tetraacrylate (PETEA) monomers in traditional liquid electrolyte, which is absorbed in a poly(3,3‐dimethylacrylic acid lithium) (PDAALi)‐coated glass fiber membrane. The well‐designed HMPE simultaneously exhibits high ionic conductivity (2.24×10^?3 S cm^?1 at 25 °C), near‐single ion conducting behavior (Li ion transference number of 0.75), good mechanical strength and remarkable suppression for Li dendrite growth. More intriguingly, the cation permselective HMPE efficiently prevents the migration of negatively charged iodine (I) species, which provides the as‐developed Li‐I batteries with high capacity and long cycling stability.     

Tuning the Chemistry of Organonitrogen Compounds for Promoting All‐Organic Anionic Rechargeable Batteries

The ever‐increasing demand for rechargeable batteries induces significant pressure on the worldwide metal supply, depleting resources and increasing costs and environmental concerns. In this context, developing the chemistry of anion‐inserting electrode organic materials could promote the fabrication of molecular (metal‐free) rechargeable batteries. However, few examples have been reported because little effort has been made to develop such anionic‐ion batteries. Here we show the design of two anionic host electrode materials based on the N‐substituted salts of azaaromatics (zwitterions). A combination of NMR, EDS, FTIR spectroscopies coupled with thermal analyses and single‐crystal XRD allowed a thorough structural and chemical characterization of the compounds. Thanks to a reversible electrochemical activity located at an average potential of 2.2 V vs. Li⁺/Li, the coupling with dilithium 2,5‐(dianilino)terephthalate (Li₂DAnT) as the positive electrode enabled the fabrication of the first all‐organic anionic rechargeable batteries based on crystallized host electrode materials capable of delivering a specific capacity of ≈27 mAh/g_electrodes with a stable cycling over dozens of cycles (≈24 Wh/kg_electrodes).     

Na[Li(NH2BH3)2]--the first mixed-cation amidoborane with unusual crystal structure

We describe the successful synthesis of the first mixed-cation (pseudoternary) amidoborane, Na[Li(NH(2)BH(3))(2)], with theoretical hydrogen capacity of 11.1 wt%. Na[Li(NH(2)BH(3))(2)] crystallizes triclinic (P1) with a = 5.0197(4) ?, b = 7.1203(7) ?, c = 8.9198(9) ?, α = 103.003(6)°, β = 102.200(5)°, γ = 103.575(5)°, and V = 289.98(5) ?(3) (Z = 2), as additionally confirmed by Density Functional Theory calculations. Its crystal structure is topologically different from those of its orthorhombic LiNH(2)BH(3) and NaNH(2)BH(3) constituents, with distinctly different coordination spheres of Li (3 N atoms and 1 hydride anion) and Na (6 hydride anions). Na[Li(NH(2)BH(3))(2)], which may be viewed as a product of a Lewis acid (LiNH(2)BH(3))/Lewis base (NaNH(2)BH(3)) reaction, is an important candidate for a novel lightweight hydrogen storage material. The title material decomposes at low temperature (with onset at 75 °C, 6.0% mass loss up to 110 °C, and an additional 3.0% up to 200 °C) while evolving hydrogen contaminated with ammonia.     

Polysulfonylamine. CLX [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 10 [2] Die dreidimensionalen Koordinationspolymere M[(CH3SO2)2N] mit M = Kalium,Rubidium, Caesium (isotype Strukturen für M = K,Rb)

Polysulfonylamines. CLX. Crystal Structures of Metal Di(methanesulfonyl)amides. 10. The Three‐Dimensional Coordination Polymers M[(CH₃SO₂)₂N], where M is Potassium, Rubidium, Cesium (Isotypic Structures for M = K, Rb) Low‐temperature X‐ray crystal structures are reported for KA (monoclinic, space group P2₁/c, Z′ = 1), RbA (isotypic and isostructural with KA), and CsA (monoclinic, P2₁/n, Z′ = 1), where A^— denotes the anion obtained by deprotonation of the strong nitrogen acid (MeSO₂)₂NH. In KA and RbA, the anion is distorted into a rare C₁ conformation, whereas the standard C₂ conformation is retained in the cesium complex. The structures consist of three‐dimensional coordination networks, in which each cation adopts an irregular (O₆N)‐heptacoordination by forming close contacts to one (O, N)‐chelating, one (O, O)‐chelating and three κ¹O‐bonding ligands; however, the coordination number for Cs⁺ is effectively increased to 8 by a very short Cs···Cs contact distance of 422.5 pm. The crystal packings of the isotypic compounds KA and RbA display lamellar layer substructures that involve six independent ligand‐metal bonds and comprise an internal cation lamella and peripheral regions built up from anion monolayers; the 3D framework is completed by one independent M—O bond cross‐linking the layer substructures. In contrast, CsA features anion monolayers that intercalate planar zigzag chains of cations (Cs···Cs alternatingly 422.5 and 487.5 pm, Cs···Cs···Cs 135.7°), whereby each chain is surrounded and coordinated by four anion stacks and each anion stack connects two cation chains. All structures exhibit close C—H···A interanion contacts consistent with weak hydrogen bonding.     

A new DMAP-catalyzed and microwave-assisted approach for introducing heteroarylamino substituents at position-4 of the quinazoline ring

We report herein a new methodology for synthesizing quinazoline derivatives bearing a heteroarylamino moiety at position-4 of the quinazoline ring. As an alternative to the Buchwald–Hartwig cross-coupling reaction, which appears, until now, as the only efficient way to react 4-chloroquinazolines with numerous amino nitrogen-containing heterocycles displaying poor nucleophilicity, we developed a DMAP-catalyzed reaction involving microwave irradiation. Optimization of the reaction conditions led to the use of 30 mol % of DMAP in toluene, using a monomode microwave reactor and sealed vials. Moreover, the S_NAr reaction intermediate salt was isolated and fully characterized. Finally, the procedure was extended to two different 2-substituted-quinazoline series and also to various anilines, demonstrating that this approach was a general efficient way to access to such 4-substituted quinazoline scaffolds of high pharmaceutical interest.     

Acetylenic and diacetylenic liquid-crystalline monomers: towards ordered conjugated polymers

Abstract

Acetylenic and diacetylenic mesomorphic monomers have been prepared in order to obtain long conjugated polymers able to give high non-linear optical hyperpolarizabilities. Here we report the synthesis of such monomers incorporating cholesteryl and methoxybiphenyl groups; their structural and thermal behaviour are described. The occurrence of mesophases in the acetylenic and diacetylenic derivatives is discussed as a function of the spacer length and of the size of the mesogen moiety. The diacetylenic derivatives containing the methoxybiphenyl groups do not exhibit any liquid-crystalline behaviour but are able to polymerize under U.V. radiation.     

Supramolecular Complexes of Multivalent Cholesterol‐Containing Polymers to Solubilize Carbon Nanotubes in Apolar Organic Solvents

Copolymers of 2‐ethylhexyl acrylate (EHA) and cholesteryloxycarbonyl‐2‐hydroxymethacrylate (CEM) were prepared by reversible addition–fragmentation chain‐transfer (RAFT) polymerization. Supramolecular complexes of these copolymers with carbon nanotubes (CNTs) were soluble in THF, toluene, and isooctane. The colloidal solutions remained stable for months without aggregation. The rationale for the choice of CEM was based on the high adsorption energy of cholesterol on the CNT surface, as computed by DFT calculations. Adsorption isotherms were experimentally measured for copolymers of various architectures (statistical, diblock, and star copolymers), thereby demonstrating that 2–5 cholesterol groups were adsorbed per polymer chain. Once the supramolecular complex had dried, the CNTs could be easily resolubilized in isooctane without the need for high‐power sonication and in the absence of added polymer. Analysis by atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) indicated that the CNTs were devoid of bundles. The supramolecular complexes could also be employed in an inverse emulsion polymerization of 2‐hydroxyethylmethacrylate (HEMA) in isooctane and dodecane, thereby leading to the formation of a continuous polymeric sheath around the CNTs. Thus, this technique leads to the formation of very stable dispersions in non‐polar organic solvents, without altering the fundamental properties of the CNTs.     

Anomalous Geomagnetic Signal Emphasized before the Mw8.2 Coastal Alaska Earthquake,Occurred on 29 July 2021

A very strong earthquake of magnitude Mw8.2 struck the coastal zone of Alaska (USA), on 29 July 2021. This earthquake was felt around the Gulf of Alaska, on a wide offshore area belonging to USA and Canada. In order to identify an anomalous geomagnetic signal before the onset of this earthquake, we retrospectively analyze the data collected on the interval 17 June–31 July 2021, via internet, at the two geomagnetic observatories, College (CMO)—Alaska and Newport (NEW)—USA, by using the polarization parameter (BPOL) and the strain effect related to geomagnetic signal identification. Thus, for both observation sites (CMO and NEW), the daily mean distribution of the BPOL and its standard deviation (STDEV) are carried out using an FFT band-pass filtering in the ULF range (0.001–0.0083 Hz). Further on, a statistical analysis based on a standardized random variable equation is applied to emphasize the following: (a) the anomalous signature related to Mw8.2 earthquake on the both time series BPOL*(CMO) and BPOL*(NEW); (b) the differentiation of the transient local anomalies associated with Mw8.2 earthquake from the internal and external parts of the geomagnetic field, taking the NEW observatory as reference. Finally, on the BPOL*(NEW-CMO) time series, carried out on the interval 7–31 July 2021, a very clear anomaly of maximum, greater than 1.2 STDEV, was detected on 22 July, with 7 days before the onset of the Mw8.2 earthquake.