Angewandte Chemie

Enantioselective synthesis of (spiro)cyclobutane derivatives poses significant challenges yet holds promising applications for both synthetic and medicinal chemistry. We report here a nickel-catalyzed asymmetric syn-hydrometalative 4-exo-trig cyclization of alkynones to synthesize alkenyl cyclobutanols with a tetrasubstituted stereocenter. This strategy features a broad substrate scope, delivering a variety of trifluoromethyl-containing rigid (spiro)carbocycle skeletons in good yields and high enantioselectivities (up to 84% yield and 98...

The X2MH6 family, consisting of an electropositive cation X and a main group metal M octahedrally coordinated by hydrogen, has been predicted to hold promise for high-temperature conventional superconductivity. Herein, we analyze the electronic structure of two members of this family, Mg2IrH6 and Ca2IrH6, showing why the former may possess superconducting properties rivaling those of the cuprates, whereas the latter does not. Within Mg2IrH6 the vibrations of the IrH64- anions are key for the superconducting mechanism, and they induce coupling in the eg* set, which are antibonding between the H 1s and the Ir dx2-y2 or dz2 orbitals...

We report a synthesis of bicyclo[2.1.1]hexanes via an intramolecular formal (3+2) cycloaddition of allylated cyclopropanes bearing a 4-nitrobenzimine substituent. Both activated and unactivated alkenes are tolerated in the transformation. The bicyclic imine products are prone to photo-induced ring opening, allowing for the epimerization of C5-stereogenic compounds.

Sulfur functional groups are ubiquitous in molecules used in the pharmaceutical and agrochemical industries, and within these collections sulfones hold a prominent position. The double aza-analogues of sulfones, sulfondiimines, offer significant potential in discovery chemistry but to date their applications have been limited by the lack of convenient synthetic routes. The existing methods mainly rely on imination of low-valent-sulfur intermediates, or the combination of pre-formed organometallic reagents and electrophilic S(VI)-functionalities...

Reprogrammable shape morphing is ubiquitous in living beings and highly crucial for them to move in normal situations, even to survive under dangerous conditions. There is increasing interest in using asymmetric hydrogel structures to understand and mimic living beings' shape morphing upon an external trigger in a controlled way. However, these asymmetric or heterogeneous configurations cannot be further modified once the polymer hydrogels are prepared. Therefore, it is a great challenge to achieve reprogrammable shape morphing using the existing hydrogels...

Artificial polymer solid electrolyte interphases (SEIs) with microphase-separated structures provide promising solutions to the inhomogeneity and cracking issues of natural SEIs in lithium metal batteries (LMBs). However, achieving homogeneous ionic conductivity, excellent mechanical properties, and superior interfacial stability remains challenging due to interference from hard-phase domains in ion transport and solid-solid interface issues with lithium metal. Herein, we present a dynamic supramolecular ion-conducting poly(urethane-urea) interphase (DSIPI) that achieves these three properties through modulating the hard-phase domains and constructing a composite SEI in situ...

The addition of polar functional groups to porous structures is an effective strategy for increasing the ability of metal-organic frameworks (MOFs) to capture CO2 by enhancing interactions between the dipoles of the polar functional groups and the quadrupoles of CO2. However, the potential of MOFs grafted to polar functional group to activate CO2 has not been investigated in the context of CO2 electrolysis. In this study, we report a mixed-ligand strategy to incorporate various functional groups in the MOFs...

The development of materials for hydrogen production via seawater electrolysis at high current densities plays a crucial role in producing renewable hydrogen energy. However, during the seawater electrolysis process, the anode inevitably undergoes chloride oxidation reaction (ClOR) due to Cl- adsorption, making the seawater electrolysis process difficult to sustain. Inspired by the selective permeability of cell membranes, we propose a biomimetic design of frustrated Lewis pairs (FLPs) layers. Combining experimental results and molecular dynamics simulations, it has been demonstrated that cerium dioxide layers with FLPs sites can decompose water molecules, capture hydroxyl anions, and repel chloride ions simultaneously...

Developing rechargeable batteries that operate within a wide temperature range and possess high safety has become necessary with increasing demands. Rapid and accurate assessment of the melting points (MPs), boiling points (BPs), and flash points (FPs) of electrolyte molecules is essential for expediting battery development. Herein, we introduce Knowledge-based electrolyte Property prediction Integration (KPI), a knowledge-data dual-driven framework for molecular property prediction of electrolytes. Initially, the KPI collects molecular structures and properties, and then automatically organizes them into structured datasets...

Solid electrolytes (SEs) in all-solid-state batteries (ASSBs) are garnering considerable attention for their potential applications in next-generation energy storage systems. Amorphous SEs with dual-anion hold great promise for achieving favorable performance, such as high ionic conductivity and good compatibility with electrodes within ASSBs. Here, we discover a family of amorphous nitride-halide SEs, Li3xMClyNx (M = Ta or La, 1 ≤ 3x ≤ 1.4, y = 5 or 3), which can achieve ionic conductivities up to 7...

Quinone compounds, with the ability to uptake protons, are promising electrodes for aqueous batteries. However, their application is limited by the mediocre working potential range and inferior rate performance. Herein, we examined quinones bearing different substituents, and for the first time introduce tetraamino-1,4-benzoquinone (TABQ) as anode material for proton batteries. The strong electron-donating amino groups can effectively narrow the band gap and negatively shift the redox potentials of quinone material...

Cluster-based spin crossover (SCO) frameworks are a new class of smart metal-organic frameworks (MOFs) with diverse structures and topologies and unique bistable physicochemical properties. Here, we report a cluster-based SCO framework [Fe3{Ag4(CN)6(H2O)}2(TPBA)3](ClO4)2·7DMF (1) with an extremely rare 3,4,6-T108 topology, in which the tripodal [Ag{Ag(CN)2}3(H2O)]2- clusters axially link the Fe2+ ions to form 2D→3D n-fold Borromean entangled networks. Under the guidance of reticular chemistry, the post-synthetic modification (PSM) from 1 with 3,4,6-T108 topology to [Fe3{Ag8X8(CN)6}(TPBA)3] (2_X, X = Cl, Br, I) with urk topology is firstly achieved via single-crystal to single-crystal (SCSC) transformation...

Achieving high enantioselectivity with synthetic receptors, particularly in water, remains a significant challenge despite the success seen in natural biological systems. In this study, we introduce a facile synthesis of Tröger's base (TB)-containing macrocyclic arenes (TBn), where TB units are linked via methylene bridges, providing the macrocycles with a rigid framework. Oxidation of enantiopure TBn yields corresponding chiral nitrogen oxides (TBnNO) with excellent water solubility, attributed to the high polarity of the N-O bond, surpassing the pH limitations of traditional ion-functionalized approaches...

Dielectric capacitors harvest energy through an electrostatic process, which enables an ultrafast charging-discharging rate and ultrahigh power density. However, achieving high energy density (Wrec) and efficiency (η) simultaneously, especially when preserving them across a wide frequency/temperature range or cycling numbers, remains challenging. In this work, by especially introducing NaTaO3 into the representative ferroelectric relaxor of Bi0.5K0.5TiO3-Bi0.5Na0.5TiO3 and leveraging the mismatch between B-site atoms, we proposed a method of enhancing local structural fluctuation to refine the polar configuration and to effectively improve its overall energy-storage performances...

Using fluorinated mono-alcohols, in particular hexafluoro-isopropanol (HFIP), as a solvent can enhance chemical reaction rates in a spectacular manner. Previous work has shown evidence that this enhancement is related to the hydrogen-bond structure of these liquids. Here, we investigate the hydrogen-bond dynamics of HFIP and compare it to that of its non-fluorinated analog, isopropanol. Ultrafast infrared spectroscopy show that the dynamics of individual hydrogen-bonds is about twice as slow in HFIP as in isopropanol...

Ultra-fast magic-angle spinning (100+ kHz) has revolutionized solid-state NMR of biomolecular systems but has so far failed to gain ground for the analysis of paramagnetic organic and inorganic powders, despite the potential rewards from substantially improved spectral resolution. The principal blockages are that the smaller fast-spinning rotors present significant barriers for sample preparation, particularly for air/moisture-sensitive systems, and are associated with lower sensitivity from the reduced sample volumes...

Photocatalytic CH4 oxidation to CH3OH emerges as a promising strategy to sustainably utilize natural gas and mitigate the greenhouse effect. However, there remains a significant challenge for the synthesis of methanol by using O2 at low temperature. Inspired by the catalytic structure in soluble methane monooxygenase (MMO) and the corresponding reaction mechanism, we prepared a biomimetic photocatalysts with the decoration of Fe2O3 nanocluster and satellite Fe single atom immobilized on carbon nitride. The catalyst demonstrates an excellent CH3OH productivity of 5...

O3-type layered oxides are highly promising cathodes for sodium-ion batteries (SIBs), however they undergo complex phase transitions and exhibit high sensibility to air, leading to subpar cycling performance and commercial viability. In this work, we report a layered cathode material (NaNi0.29Cu0.1Mg0.05Li0.05Mn0.2Ti0.2Sn0.11O2) with a sate-of-the-art high-entropy compositional design. We unveil that such a configuration featuring inhomogeneous coordination environment of transition metal (TM) elements, can enable enhanced gliding energy (-0...

The discovery of efficient and stable electrocatalysts for the oxygen evolution reaction (OER) in acidic conditions is crucial for the commercialization of proton-exchange membrane water electrolyzers. In this work, we propose a Sr(OH)2-assisted method to fabricate a (200) facet highly exposed strontium-doped IrOx catalyst to provide available adjacent iridium sites with lower Ir-O covalency. This design facilitates direct O-O coupling during the acidic water oxidation process, thereby circumventing the high energy barrier associated with the generation of *OOH intermediates...

After half a century from their isolation in 1974, we report the first total syntheses of β- and γ-naphthocyclinones, two dimeric pyranonaphthoquinones featuring an unusual bicyclo[3.2.1]-octadienone core. The syntheses were achieved with full stereochemical control and functional group management, relying on 1) enantioselective construction of the bicyclic core by Rh-catalyzed enantioselective 1,4-addition followed by thiolate-mediated reductive cyclization, and 2) judicious design of a common chiral, non-racemic monomer unit that is capable of divergence into the donor and acceptor units, and reunion to construct the bicyclo[3...