Zou H, Qi J, Wang X
… +7 more, Ma Y, Ma Y, Du Y, Li J, Jiang Z, Yu ZZ, Qiu J
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42376790
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Clean energy demands and zero-carbon commitments have stimulated the desire for stable seawater electrolysis, yet device corrosion and catalyst deactivation seriously hinder industrial-scale deployment. Here we present a...Clean energy demands and zero-carbon commitments have stimulated the desire for stable seawater electrolysis, yet device corrosion and catalyst deactivation seriously hinder industrial-scale deployment. Here we present an innovative integrated platform that couples photothermal evaporation and desalinated water electrolysis. Relying on a hydrogen-bonding crosslinking mechanism and anion-induced Hofmeister effects, a lightweight spherical evaporator uniformly coated with a modified needle coke gel film is designed, exhibiting attractive continuous desalination performance (2.32 kg m h in 3.5 wt%) and salt-resistant self-cleaning capabilities. Subsequently, two independently improved evaporation-collection systems outperform the traditional configuration during extended all-weather outdoor experiments. Especially, the gas-stripping assisted evaporation system holds powerful resistance capacity to adverse weather, achieving 5 times more water yield on a rainy day. Importantly, their seamless adaptation to anion/cation exchange membrane electrolysis systems has pioneered the long-term application of advanced membrane electrodes in desalinated water electrolysis, cleverly addressing corrosion and catalyst deactivation barriers. This integrated strategy provides a practicable route for energy-saving and large-scale hydrogen extraction from seawater.
Yang L, Zhao Z, Gai S
… +8 more, Zang P, Yang M, Yu C, Gong H, Yan W, Xie Y, Tang Y, Lin J
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42376788
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Photothermoelectric catalytic therapy (PTECT) faces challenges like restricted thermoelectric activity and tumor recurrence. In this study, we introduce a defect engineering strategy to synthesize sulfur vacancies (S) en...Photothermoelectric catalytic therapy (PTECT) faces challenges like restricted thermoelectric activity and tumor recurrence. In this study, we introduce a defect engineering strategy to synthesize sulfur vacancies (S) enriched CuSnS nanosheets with promising thermoelectric properties, followed by loading small-molecule inhibitor NLG919. Spherical aberration corrected transmission electron microscopy and X-ray absorption fine structure reveal the fine structural characteristics of S, which make the nanosheets possess an ultra-high photothermal conversion efficiency of 64.7% under 808 nm laser irradiation. This generates a localized temperature gradient that induces an internal electric field, which enhances carrier separation, boosts peroxidase- and catalase-like activities, and produces substantial amounts of reactive oxygen species (ROS), enabling cooperative PTECT and multi-enzymatic catalytic therapy. Density functional theory calculations show that S reduces the thermal conductivity, thus enhancing the figure of merit value and the PTECT effect. Accumulation of Cu ions, ROS, and heat triggers cuproptosis, mitochondrial apoptosis, and endoplasmic reticulum-based immunogenic cell death. The released NLG919 disrupts the IDO-induced Trp/Kyn metabolic pathway, reversing the tumor immune suppressive microenvironment. This integrated approach achieves high efficiency (96%) and long-term anticancer efficacy. These findings may provide valuable insights for advancing thermoelectric materials in tumor therapy.
Wilmshurst AM, Jo T, Kerridge RL
… +7 more, Sangolkar AA, Ling Z, Buchanan A, Wells N, Ben-Tal Y, Crespi S, Williams GT
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42376784
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Photoswitches provide the opportunity to remotely and precisely control matter on the nanoscopic scale. For many materials and biological applications, photoswitches with long wavelength response are essential; however,...Photoswitches provide the opportunity to remotely and precisely control matter on the nanoscopic scale. For many materials and biological applications, photoswitches with long wavelength response are essential; however, few switches offer inherent response to red/near infra-red light. Previous works have described the use of intermolecular interactions as a method to redshift the activation wavelength of photoswitches and to improve thermal half-life. However, these systems are limited in their application due to the inherent bimolecularity of this strategy preventing its use in dilute or complex environments. Herein, we describe the use of topologically constrained supramolecular interactions to improve the switching properties of an indigo photoswitch within a [2]-rotaxane. This enabled photoswitching with 730 nm light, as well as a 100-fold increase in thermal half-life and double the population of the metastable state under constant irradiation. This surpasses previous attempts at using supramolecular interactions to increase the thermal half-life by >10-fold. This novel strategy towards the redshifting and fine-tuning of these molecular photoswitches has implications for the design of molecular machines and applied switching technologies. We anticipate that our insights into the design of such molecules will unlock new applications for mechanically interlocked molecules.
Wang SQ, Yang Y, Chen YP
… +8 more, Yan C, Cao XK, Xue ZQ, Wang H, Zhao QR, Chen X, Huang JQ, Zhang Q
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42376776
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Hard carbon (HC) anode in sodium-ion batteries suffer from low initial Coulombic efficiency and irreversible capacity loss, limiting practical energy density and cycle life of SIBs. While direct-contact presodiation of H...Hard carbon (HC) anode in sodium-ion batteries suffer from low initial Coulombic efficiency and irreversible capacity loss, limiting practical energy density and cycle life of SIBs. While direct-contact presodiation of HC has been proposed to increase the initial Coulombic efficiency of SIBs, but its low utilization efficiency can cause residual Na on the HC surface, resulting in rapid degradation and even safety concerns. Herein, we proposed a soft-contact presodiation (SCP) method, which can remove and recycle Na source and therefore greatly improve the utilization of the Na source and safety of SIBs. The SCP-treated HC anode achieves a ≈30.0% increase in ICE when paired with a NaNiFeMnO cathode, while maintaining minimal temperature rise (ΔT≈1.3°C) during treatment. The resulting SCP-HC exhibits exceptional thermal stability with negligible exothermic activity at 125.0°C and remains chemically stable for over 3.0 days. Through multimodal analysis, we reveal an adsorption-dominated compensation mechanism where replenished Na participates in solid electrolyte interphase formation while simultaneously occupying adsorption sites as metallic clusters. The pouch cell incorporating SCP-HC anode delivers 90.6% ICE and retains 80.0% capacity after 150 cycles. This work establishes a safe, efficient, and economically viable presodiation platform that paves the way for practical high-energy sodium-ion batteries.
Jones CF, Hood BR, de Coene Y
… +5 more, Kearns H, Faulds K, Champagne B, Clays K, Fielden J
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42376774
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Electrochemical switch-on of second-order non-linear optical (NLO) responses (β) has been demonstrated in a polyoxometalate (POM) based chromophore (POMophore) for the first time. Reduction of the POM in a POM-imidoaryl-...Electrochemical switch-on of second-order non-linear optical (NLO) responses (β) has been demonstrated in a polyoxometalate (POM) based chromophore (POMophore) for the first time. Reduction of the POM in a POM-imidoaryl-NO derivative invokes an up to 15-fold off/on switchable increase in intensity of scattered frequency-doubled light, and the highest "on" state β yet reported for a redox-cyclable POMophore. Computational and spectroscopic studies show that in the oxidized state, directionally opposed charge transfer (CT) transitions to POM and ─NO result in a low net β. Upon reduction, the POM becomes a much weaker CT acceptor, resulting in more dipolar imido-aryl to nitro CT, and thus enhanced NLO response.
Orozco C, Stewart OC, Vanagas N
… +5 more, Morrison G, Loye HZ, Smith HE, Knope K, Stoll SL
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42376754
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We report the synthesis and characterization of a series: UOS, UOSe and β-US, the first examples of uranium-chalcogen-containing nanomaterials using colloidal synthetic techniques. The challenge to these syntheses is the...We report the synthesis and characterization of a series: UOS, UOSe and β-US, the first examples of uranium-chalcogen-containing nanomaterials using colloidal synthetic techniques. The challenge to these syntheses is the oxophilicity of uranium, as uranium dioxide is difficult to avoid and the only actinide nanomaterial reported previously. All reagents, the metal, chalcogen source and solvent, were investigated to understand phase formation in solution. We found a post-synthetic modification, commonly known as digestive ripening, that led to size control of the β-US nanoparticles. The phases were confirmed using powder x-ray diffraction and Rietveld analysis, as well as microscopy ( transmission electron microscopy), and magnetic susceptibility measurements. The oxychalcogenide nanomaterials are antiferromagnetic, in contrast to previously reported UO nanoparticles. As found in bulk β-US, the nanoparticles are paramagnetic, with a moment consistent with localized f electrons.
Zhao Y, Tomasini M, Göttker-Schnetmann I
… +3 more, Falivene L, Caporaso L, Mecking S
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42376753
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In-chain functional groups can reduce the environmental impact of polyethylene waste and enhance its recyclability. A significant advance was the realization of the long-sought catalytic copolymerization of carbon monoxi...In-chain functional groups can reduce the environmental impact of polyethylene waste and enhance its recyclability. A significant advance was the realization of the long-sought catalytic copolymerization of carbon monoxide with ethylene in a non-alternating manner, providing keto-polyethylene materials with low densities of photodegradable keto groups in the chain. Despite this breakthrough, the state-of-the-art catalysts' limited carbon monoxide tolerance is a hurdle in further developing more sustainable polyethylenes. Here we show how these fundamental issues can be addressed by implementation of attractive Ni···O interactions in novel as well as state-of-the-art neutral nickel catalyst motifs. Incorporation of P-bound 2,6-diphenoxyphenyl moieties into both phosphine-imidate and phosphine-phenolate ligand frameworks provides highly active and robust catalysts that generate keto-polyethylenes not accessible to date. Theoretical calculations reveal that Ni···O interactions lower cis/trans isomerization barriers of coordinated ethylene, thereby driving ethylene insertion along the desired non-alternating pathway. At the same time, steric constraint raises the energy barriers for carbon monoxide insertion and reductive elimination, effectively suppressing undesired extensive carbon monoxide insertion and catalyst deactivation. The concept uncovered enables operating conditions, productivities and in-chain functional group concentrations not possible with existing catalysts, and provides perspectives for putting much needed environmentally benign polyolefins into practice.
Zhang X, Ding Q, Yi X
… +10 more, Hui Q, Gu YH, Fu J, Lu K, Li D, Fang C, Xu Y, Yuan S, Wang W, Zhang Z
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42376751
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Trace removal of hexafluoropropylene (CF) from octafluoropropane (CF) is crucial for producing high-purity fluorinated electronic gases, yet it remains highly challenging because of their similar molecular dimensions. He...Trace removal of hexafluoropropylene (CF) from octafluoropropane (CF) is crucial for producing high-purity fluorinated electronic gases, yet it remains highly challenging because of their similar molecular dimensions. Here, we report an electronically driven pore-engineering strategy for CF/CF separation, in which Jahn-Teller-active Cu directs framework reconstruction from the large-aperture channels of ZnTPO (HTPO = tris(4-carboxyphenyl) phosphine oxide) to the narrow cage-like pore network of CuHTPO, thereby switching the separation behavior from co-adsorption to molecular sieving. Consequently, CuHTPO delivers > 99.999% pure CF with productivities of 314.9 and 2819 L kg from 1/9 and 1/99 CF/CF mixtures, respectively. Optical imaging at the single-particle level directly visualizes the rapid transport of CF through the channels, while single-crystal X-ray diffraction, FTIR spectroscopy, and molecular simulations collectively elucidate the structural origin of the electronically regulated sieving behavior. Taken together, this work positions electronic-structure-directed pore reconstruction as a powerful material-design strategy for programming confined pore spaces, enabling robust and recyclable molecular sieving of closely related gases.
Wang HJ, Liu Y, Wang Y
… +11 more, Xing Y, Jiang T, Yang C, Song B, Dai X, Dou J, Zhang X, Li L, Wu H, Hu W, Stoddart JF
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42376747
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Bioimaging technology is a fundamental platform for visualizing biological processes and guiding clinical interventions. Consequently, developing effective strategies for constructing biocompatible, long-wavelength emiss...Bioimaging technology is a fundamental platform for visualizing biological processes and guiding clinical interventions. Consequently, developing effective strategies for constructing biocompatible, long-wavelength emissive, and intrinsically selective bioprobes has long been a central goal in chemistry. Herein, we develop a stepwise assembly protocol to construct an exotic cage-in-rings bioimaging probe, TPBCage⊂3CB[8], through noncovalent association of a hexacationic cage (TPBCage) with cucurbit[8]uril (CB[8]). The complex adopts a thermodynamically favored C-symmetrical conformation rather than the expected C-symmetrical analogue. It preserves two exposed pyridinium units, providing a structural basis for efficient cellular uptake, while the other four pyridinium units are partially shielded by CB[8], reducing nonspecific interactions in bioimaging to some extent compared with the free cage. Encapsulation by CB[8] effectively suppresses π-π stacking of the cage, improving its aqueous solubility. Concomitantly, CB[8] encapsulation narrows the energy gap of the cage, resulting in a red shift in emission from 552 to 652 nm and an enhanced fluorescence quantum yield. Benefiting from enhanced water solubility, good biocompatibility, and deep-red emission, the complex enables lysosome-selective imaging in deep-red region. This work establishes an alternative supramolecular strategy for subcellular-selective imaging, in which cage-in-rings confinement enables control over excited-state properties, enabling the development of intrinsically selective bioimaging probes.
Lei Y, Liu R, He Y
… +10 more, Luo G, Liu C, Su J, Li B, Long X, Tan Y, Luo Y, Qiu H, Huang Y, Lu Z
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374966
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Persistent thermally activated delayed fluorescence (p-TADF) is fundamentally constrained by the kinetic trade-off between reverse intersystem crossing (rISC) and triplet exciton decay, including phosphorescence and non-...Persistent thermally activated delayed fluorescence (p-TADF) is fundamentally constrained by the kinetic trade-off between reverse intersystem crossing (rISC) and triplet exciton decay, including phosphorescence and non-radiative processes, which intrinsically limits its lifetime (τ). Here we present a synergistic strategy that overcomes this limitation by concurrently slowing the rISC rate (k) while preserving the condition k ≫ k + k and deliberately promoting multiple intersystem crossing (ISC)/rISC exciton cycles. The efficacy of this approach is validated by o-TFBCz, which achieves an unprecedented τ of 1.00 s even in unannealed poly(methyl methacrylate), despite originating from a phosphorescence core with a lifetime (τ) of only 1.92 s. This system exhibits bluish-green afterglow under blue-light excitation and outstanding thermal stability. Quantitative photophysical analysis reveals an average of 2.1 ISC/rISC cycles per exciton in this material, enabled by an ISC rate (k) that dominates over fluorescence (k) and internal conversion (k) rates (k > k + k). These results establish a clear, generalizable blueprint for breaking the lifetime ceiling of pure organic p-TADF materials.
Qian L, Dean C, Kochetkov I
… +3 more, Chen H, Huang Y, Nazar L
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374964
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Sulfide solid electrolytes (SEs) are excellent candidates for solid-state batteries (SSBs), but their extreme sensitivity to moisture and lack of oxidative stability with uncoated high-voltage cathodes incur processing c...Sulfide solid electrolytes (SEs) are excellent candidates for solid-state batteries (SSBs), but their extreme sensitivity to moisture and lack of oxidative stability with uncoated high-voltage cathodes incur processing complexity and cost. Here, we present a simple and cost-effective decanoate fatty-acid (DA) coating strategy for argyrodite (LiPSCl, LPSCl) that stabilizes it to exposure at 39% relative humidity for up to 2 h, while preserving its structure, ionic conductivity, and increasing its anodic stability. Cells employing 2 wt%-coated LPSCl (DA-LPSCl) as the catholyte, with a bare NCM85 cathode and Li-In anode, deliver a capacity of 175 mAh.g, and 96% capacity retention over 150 cycles at 0.2 C, while bare LPSCl retains only 61% capacity. Symmetric Li|DA-LPSCl|Li cells cycle for 1000 h, in contrast to bare LPSCl cells, which short-circuit after ∼230 h. Moreover, full cells using a lithium metal anode with the DA-LPSCl SE showed remarkable performance compared to state-of-the-art SSBs, retaining 81% of their capacity after 300 cycles at 0.2 C. High-loading cells with areal capacities up to 3.2 mAh cm are also demonstrated. This work showcases the potential of a low-cost, processable, and flexible coating to address key limitations of sulfide SEs, advancing the commercial viability of SSBs.
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374958
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Strategic microenvironment engineering of single-atom catalysts offers a method for simultaneously enhancing oxygen reduction reaction (ORR) activity and stability. Herein, we synthesize Fe single atoms on an S-doped hol...Strategic microenvironment engineering of single-atom catalysts offers a method for simultaneously enhancing oxygen reduction reaction (ORR) activity and stability. Herein, we synthesize Fe single atoms on an S-doped hollow carbon matrix with carbon vacancies (Fe SAs/NSC) via a topological transformation strategy. The resulting Fe SAs/NSC exhibits exceptional ORR performance and enables aqueous zinc-air batteries (ZABs) with remarkably highpower density. In situ spectroscopic analyses confirm that S heteroatoms in the second coordination shell of FeN sites, along with adjacent carbon vacancies, collectively accelerate the conversion of oxygenated intermediates and simultaneously stabilize the FeN active site configuration of Fe SAs/NSC. Theoretical calculations further reveal that introduced S species and adjacent carbon vacancies cooperatively fine-tune the hybridization of Fe 3d and O 2p orbitals, increasing the occupancy of antibonding orbitals near the Fermi level and thereby promoting *OH desorption. Meanwhile, this heteroatom-defect synergy strengthens the anchoring of Fe sites within the carbon matrix and enhances the thermodynamic stability of these sites, indicating robust resistance to demetallation under operating conditions. Overall, this work establishes atomic-level heteroatom-defect cooperation as an effective strategy for the concurrent optimization of activity and stability in multi-electron electrocatalysis.
Natho P, Vicenti A, Colella M
… +7 more, Pasca F, Romanazzi G, Niso M, Abate C, Mesto E, Schingaro E, Luisi R
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374957
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Strained spiro heterocycles have gained popularity in medicinal chemistry due to their potential to act as conformationally rigid non-classical three-dimensional bioisosteres. Recently, 1-azaspiro[3.3]heptane has been va...Strained spiro heterocycles have gained popularity in medicinal chemistry due to their potential to act as conformationally rigid non-classical three-dimensional bioisosteres. Recently, 1-azaspiro[3.3]heptane has been validated as a piperidine bioisostere, although synthetic methods available for functionalized or heteroatom-containing derivatives are scarce. We address this shortcoming by accessing spirocyclic 1-azabicyclo[1.1.0]butanes-a novel class of "super-strained" spirocycles-through a Johnson-Corey-Chaykovsky reaction between cyclobutane-, oxetane-, and azetidine-substituted sulfonium salts, and azirines. We demonstrate that such spirocycles are suitable precursors for highly functionalized 1-azaspiro[3.3]heptane derivatives. In addition, such super-strained spirocycles have been validated in vitro as potential sigma-1 receptor agonists, a target identified through an artificial intelligence-supported target fishing approach.
Han Z, Wang KY, Huo J
… +6 more, Rushlow J, Liu Z, Yang Y, Liang RR, Shi W, Zhou HC
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374956
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Enantioselective recognition is vital for numerous chemical and biological applications, which, however, remains challenging due to the nearly indistinguishable physicochemical properties of enantiomers. In this study, w...Enantioselective recognition is vital for numerous chemical and biological applications, which, however, remains challenging due to the nearly indistinguishable physicochemical properties of enantiomers. In this study, we report a luminescent sensing strategy for enantioselective recognition based on metal-organic frameworks (MOFs) constructed through chiral linker exchange, which simultaneously introduces chirality and defective sites into the frameworks. The resulting chiral defective MOFs exhibit confined nanopore environments, resulting in distinct luminescence responses toward enantiomers. A pair of enantiomeric MOFs was constructed, exhibiting opposite selective recognition performance toward R- and S-substrates. The sensing behavior arises from the interplay of competitive absorption and electron transfer process, while disparities in binding affinities serve as the dominating factor dictating the enantioselectivity. Meanwhile, this system enables the quantitative detection of enantiomeric excess (ee) values in mixtures through differential luminescence responses. Due to its facile synthesis routes, selectivity, and ease of implementation, this strategy offers a practical approach for developing chiral luminescent sensing materials, while highlighting the significance of host-guest interactions in sensing.
Xia Q, Gao X, Gong S
… +6 more, Wu J, Liao Y, Zhai Y, Li W, Zhou Y, Zhang X
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374943
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Sulfite (SO ), abundant in industrial wastewater, poses environmental challenges due to its instability, oxygen scavenging, and microbial toxicity. However, current sulfite treatment methods primarily focus on oxidation...Sulfite (SO ), abundant in industrial wastewater, poses environmental challenges due to its instability, oxygen scavenging, and microbial toxicity. However, current sulfite treatment methods primarily focus on oxidation to inert sulfate or biological reduction, both of which suffer from low efficiency, secondary emissions, or loss of sulfur value. In this study, we present a sustainable electrocatalytic strategy for upgrading sulfite-laden wastewater by directly converting SO into value-added sulfonates under ambient conditions. Using commercial Ni catalysts and methanol as a representative feedstock, the system achieves a sulfite-to-sulfonate conversion ratio exceeding 90% after 3 h of continuous electrolysis, with a maximum sulfonate production rate of 7870 µmol cm h at 1000 mA cm, highlighting efficient upgrading of sulfite-laden wastewater into organosulfur products. To enable continuous system operation, Ni nanoparticles were incorporated into a carbon nanotube (CNT)-based electrochemical membrane, which shows a sulfite removal ratio above 93% and a sulfite-to-sulfonate conversion ratio above 90%, demonstrating suitability for scalable wastewater treatment and sulfur valorization. Moreover, techno-economic analysis reveals a minimum levelized production cost of $300.84 per ton at 400 mA, corresponding to an 79.85% reduction compared with conventional routes. This integrated electrocatalytic membrane system offers a promising route for coupling sulfite removal with organosulfur synthesis.
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374942
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Oxidative coupling of methane (OCM) into ethylene is a very promising process for the valorization of methane. However, the high operating temperatures, severe exothermicity, and poor selectivity at high conversion rates...Oxidative coupling of methane (OCM) into ethylene is a very promising process for the valorization of methane. However, the high operating temperatures, severe exothermicity, and poor selectivity at high conversion rates have hindered its industrialization. Measurements of local catalyst temperatures, let alone research into the determining experimental parameters, are still scarce. Here, we use operando luminescence thermometry (LT) to measure local catalyst temperatures during the OCM reaction. This analytical technique reveals catalyst temperatures exceeding the oven temperature under inert conditions by almost 250°C. We observe a dependence of the local catalyst temperature on the amount of heat generated by the OCM process, and we show that the heat transfer and resulting catalyst temperature in the reactor are strongly influenced by experimental conditions and reactor/catalyst dimensions. This work showcases the opportunities of LT to measure catalyst temperatures and get more insight into high-temperature catalytic processes and their heat management, leading to crucial insights for the further optimization of chemical processes, such as OCM.
Wang C, Hu X, Zhang M
… +6 more, Liu R, Zhu Y, Lu X, Xu S, Liu G, Tan C
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374940
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Developing confined supramolecular environments capable of regulating radical cascade processes with high site selectivity remains a longstanding challenge in catalysis. Herein, we report two imidazolium-functionalized c...Developing confined supramolecular environments capable of regulating radical cascade processes with high site selectivity remains a longstanding challenge in catalysis. Herein, we report two imidazolium-functionalized cationic covalent organic cages featuring distinct cavity architectures, including a triangular-prismatic cavity (cage 1) and a bowl-shaped cavity (cage 2), as confined platforms for oxidant-free Hofmann-Löffler-Freytag (HLF)/cyclization cascade catalysis. Both cages efficiently mediate a one-pot transformation of N-chloroamides into pyrrolidine derivatives under mild conditions, whereas cage 1 exhibits substantially enhanced activity and selectivity relative to cage 2 and a monomeric analog. Mechanistic investigations suggest that the geometrically confined cationic cavity of cage 1 promotes substrate preorganization through cooperative host-guest interactions, stabilizes nitrogen-centered radical intermediates via electrostatic and C-H···π interactions, and facilitates the key 1,5-hydrogen atom transfer (1,5-HAT) process by lowering the associated activation barrier. Host-guest binding studies and DFT calculations, reveal a structure-recognition-reactivity relationship in which substrate anchoring, spin delocalization, and cavity confinement collectively govern catalytic efficiency. These findings demonstrate how confined cationic microenvironments can reconstruct radical cascade pathways and provide a general strategy for designing supramolecular catalysts for selective multistep transformations.
Bi H, Zhao Z, Yang Q
… +5 more, Zhang B, Zhang R, Wang X, Yu C, Qiu J
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374937
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Publisher ↗
Efficient ion desolvation and rapid mass transport are crucial yet often competing requirements for stabilizing Zn anodes in aqueous Zn-ion batteries. This dilemma arises because ion desolvation introduces additional ene...Efficient ion desolvation and rapid mass transport are crucial yet often competing requirements for stabilizing Zn anodes in aqueous Zn-ion batteries. This dilemma arises because ion desolvation introduces additional energy barriers that increase ion diffusion resistance. To reconcile this inherent trade-off, a hydrogen-bonded organic framework (HOF) based on C‑symmetric trigonal carboxyl ligands is engineered as an ion-sieving interface. This design integrates precise pore size control with tailored chemical environment to regulate Zn desolvation behavior. As expected, the flexible HOF incorporating an electron-deficient triazine core (HOF-TAT) dynamically strips solvated water molecules while maintaining continuous ion flux. This process fosters a gradient solid electrolyte interphase that synergizes with the self-adaptive porous framework to guide dense (101)-oriented Zn deposition. The HOF-TAT@Zn symmetric cells stably cycle exceeding 3400 h at 5 mA cm. Furthermore, the iodophilic porous framework immobilizes shuttling polyiodides through strong physicochemical interactions. When integrated with an ultrathin Zn anode (10 µm), the Zn-iodine batteries deliver a high-rate capacity (142.2 mAh g at 5 A g) and long-term lifetime (50 000 cycles). This work offers an intelligent strategy to concurrently overcome the high energy barriers of ion desolvation and the kinetic limitations of ion transport for building advanced electrochemical devices.
Zhou L, Chen H, Liang Y
… +4 more, Rao H, Wang L, Kuang M, Yang J
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374932
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The selective electroreduction of CO to n-propanol is fundamentally constrained by sluggish C─C coupling and the instability of key oxygenated intermediates. Here, we propose a quasi-tandem catalytic strategy enabled by...The selective electroreduction of CO to n-propanol is fundamentally constrained by sluggish C─C coupling and the instability of key oxygenated intermediates. Here, we propose a quasi-tandem catalytic strategy enabled by defect-rich amorphous ZrO, where the amorphous oxide-metal interfacial environment promotes *CO generation, stabilization of oxygenated C intermediates (*OCCOH), and subsequent C─C coupling toward n-propanol formation. The resulting catalyst, composed of amorphous ZrO, Cu, and Ag, delivers a Faradaic efficiency of 23.2% ± 1.6% and a partial current density of 50.6 mA cm for n-propanol, representing more than 2.5- and 3.5-fold enhancements, respectively, compared to its crystalline ZrO analogue. Density functional theory (DFT) calculations reveal that the amorphous ZrO─Cu interface, not only enhances the formation of *COH, but also significantly lowers the energy barriers for *CO-COH coupling and *CO-*OCCOH coupling toward n-propanol generation. These findings establish amorphous oxide-metal interfacial engineering as an effective strategy for quasi-tandem catalysis, enabling cooperative multistep C─C coupling pathways toward selective C electrosynthesis from CO.
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374930
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Publisher ↗
While the chemistry of ring-opening polymerization has advanced significantly to alleviate the escalating plastic waste crisis, highly selective and efficient catalysts to synthesize chemically recyclable, high-performan...While the chemistry of ring-opening polymerization has advanced significantly to alleviate the escalating plastic waste crisis, highly selective and efficient catalysts to synthesize chemically recyclable, high-performance polythioesters remain needed. Typical ring-opening catalysts, however, face an intrinsic stereochemical challenge: unavoidable monomer racemization due to elevated α-hydrogen acidity, which severely hampers the synthesis of highly tactic crystalline materials and diminishes the performance of the resulting plastics. Here, we report the design and synthesis of a covalent borane-thiourea organocatalyst for the stereoselective ring-opening polymerization of enantiopure dithiolactones. Through incorporation of a strongly Lewis acidic 9-borafluorene moiety, this metal-free system effectively reduces the basicity of propagating thiolate chain ends while enabling thiourea-mediated monomer activation, thereby ensuring rapid polymerization with minimal racemization. Consequently, this approach affords polythioesters with near-perfect isotacticity (P = 0.97) and high molecular weights (M up to 58.1 kDa). Notably, the resulting stereoregular polymers are tough, semicrystalline materials with properties comparable to commercial polyolefins like low-density polyethylene, while exhibiting complete chemical recyclability to realize a sustainable cradle-to-cradle closed loop. Overall, this covalent borane-thiourea organocatalyst solves the intrinsic stereochemical challenges in typical ring-opening polymerizations, providing a powerful strategy to access chemically recyclable and tough thermoplastics from dithiolactones as promising next-generation sustainable polymers.