Zhang YM, Li YR, Shi Y
… +6 more, Zheng XJ, Guo SM, Mo Z, Huang G, Xie JH, Zhou QL
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374928
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Rational design of chiral ligands with precisely tailored steric and electronic properties is pivotal to advancing asymmetric transition-metal catalysis. Despite their promising strong σ-donating ability, sp-hybridized c...Rational design of chiral ligands with precisely tailored steric and electronic properties is pivotal to advancing asymmetric transition-metal catalysis. Despite their promising strong σ-donating ability, sp-hybridized carbanion ligands have long been underexplored owing to the inherent instability of C(sp)-metalated complexes. In this study, we report a modular design of chiral spiro monophosphine ligands ((R)-SciPhos) integrating an electronic-withdrawing group, a quaternary carbon moiety, and a rigid spiro scaffold, which efficiently addresses this long-standing challenge. This judicious design enables the synthesis of bench-stable neutral C(sp),P-chelated iridium complexes via intramolecular C─H activation. These novel iridacycle catalysts exhibit high efficiency, excellent enantioselectivity, and a broad substrate scope in the asymmetric hydrogenation of challenging β,β-disubstituted sodium acrylates, achieving up to 99% yield and 97% ee with a turnover number (TON) of 5000. Mechanistic studies reveal an Ir(III)/Ir(V) catalytic cycle involving an olefin dihydride iridium(III) intermediate, wherein the migratory insertion step dictates enantioselectivity via noncovalent interactions. This work establishes a general platform for C(sp)-metalated complex-based catalysis, opens new avenues for the development of innovative asymmetric catalytic systems, and unlocks access to previously inaccessible enantioselective transformations.
Li X, Zheng Y, Guo J
… +9 more, Cao L, Hou J, Zhang Y, Zhang L, Cheng N, Ge B, Zhang B, Wei Z, Sun SG
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374925
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Room-temperature sodium-sulfur (RT Na─S) batteries offer high theoretical energy density and low cost, yet their practical performance is fundamentally limited by sluggish sulfur redox kinetics, particularly the intertwi...Room-temperature sodium-sulfur (RT Na─S) batteries offer high theoretical energy density and low cost, yet their practical performance is fundamentally limited by sluggish sulfur redox kinetics, particularly the intertwined kinetic limitations of late-stage NaS→NaS→NaS conversions. Here, we propose a step-targeted tandem catalysis strategy that integrates atomically dispersed Fe-N sites with polar ZrO nanodomains within a conductive carbon host to precisely regulate the rate-determining sulfur conversion cascade. Density functional theory reveals a step-specific catalytic sequence, in which Fe-N preferentially lowers the activation barrier for NaS→NaS conversion, while ZrO thermodynamically drives the subsequent NaS→NaS step. Their electronic coupling creates a continuous activation landscape that accelerates the entire solid-solid reaction cascade. Experimental kinetic analyses corroborate this mechanism, showing reduced polarization, enhanced surface-controlled kinetics, and mitigated transport limitations. As a result, the tandem-catalyzed Na─S cathode delivers an initial capacity of 1408 mAh g, ultralong cycling stability over 10 000 cycles at a high current density of 5 A g, and robust operation at -20°C. This work establishes tandem catalysis as an effective design paradigm for precisely regulating multistep sulfur conversion reactions in Na─S batteries.
Li R, Zhao Y, Tian JJ
… +4 more, Quinn EC, Gao Y, Gace MT, Chen EY
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374923
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Incorporation of functional groups into poly(3-hydroxyalkanoate)s (PHAs) is an important strategy to tailor their properties for specific applications, but both scopes of functional groups and the methods of transforming...Incorporation of functional groups into poly(3-hydroxyalkanoate)s (PHAs) is an important strategy to tailor their properties for specific applications, but both scopes of functional groups and the methods of transforming them into tailored PHA materials are currently limited and merit further exploration. Here, we report a catalyst-controlled stereoselective ring-opening polymerization of functionalized propiolactones for the synthesis of vinyl-, allyl-, and propargyl-functionalized PHAs with high syndiotacticity (P up to 0.95) and a broad glass and melting transition window (T down to -31°C, T up to 126°C). Copolymerization of such lactones with β-butyrolactone further enhances PHA's thermal robustness and mechanical toughness. Three different methods have been developed to further transform the functionalized PHAs into creep- and solvent-resistant crosslinked PHA thermosets, dynamic-supramolecular elastomeric PHA networks, and grafted PHAs with hydrophilic and bioactive molecules. PHA functionalization, also uncovers a rare example of PHA supramolecular stereocomplexes via blending an enantiomeric, vinyl-functionalized PHA pair.
Liu Y, Zhou H, Guo J
… +8 more, Wang HQ, Song J, Li Z, Ding L, Tian Q, Liu Q, Fan B, Guo X
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374922
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Dion-Jacobson (DJ) phase 2D perovskites have attracted much interest in photovoltaic community owing to their potential higher stability relative to 3D counterparts. The conventional wisdom has been that organic diammoni...Dion-Jacobson (DJ) phase 2D perovskites have attracted much interest in photovoltaic community owing to their potential higher stability relative to 3D counterparts. The conventional wisdom has been that organic diammoniums certainly generate DJ 2D perovskites by forming bilateral hydrogen bonds with two layers of inorganic [PbI] slabs. However, we herein report a diammonium-based non-DJ phase 2D perovskite, composed of 3,3'-methylenediphenyldiammonium (3,3-MDPDA). Single-crystal structure of the resultant 2D perovskite has a formula of (3,3-MDPDA)PbI as the DJ phase, but reveals that there are two layers of 3,3-MDPDA between adjacent inorganic layers and two ammonium groups of each 3,3-MDPDA link to a single inorganic [PbI] slab. Moreover, the 3,3-MDPDA cations in the organic bilayer present unique π-π interactions, including intralayered edge-to-face and interlayered parallel-displaced configurations, respectively, leading to high stability of the diammonium-based non-DJ 2D perovskite. When introducing it into the 3D perovskite film to construct 2D/3D structures, resulting perovskite solar cells and modules (effective area: 50 cm) demonstrate efficiencies of 26.52% and 23.34%, respectively, with outstanding operational stability retaining 94% of initial efficiency under continuous maximum power point tracking for 1200 h.
Lv D, Zhang X, Cheng L
… +4 more, Yu J, Liu Y, Wang HG, Zhu G
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374915
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The development of solid-state lithium metal batteries (SSLMBs) is severely restricted by the inherent drawbacks of conventional solid electrolytes, including sluggish ionic conduction and unstable solid electrolyte inte...The development of solid-state lithium metal batteries (SSLMBs) is severely restricted by the inherent drawbacks of conventional solid electrolytes, including sluggish ionic conduction and unstable solid electrolyte interphase (SEI). Herein, we propose a strategy for constructing vinylene-linked covalent organic framework (COF)-based porous composite polymer electrolytes (TFP-COF@PNFs CPEs). The strongly polar -C≡N and -F moieties in TFP-COF form prominent ion-dipole interactions with Li, which reduce the dissociation energy barrier of Li salts, guide the oriented transport of Li, and induce the formation of stable SEI. Therefore, the optimized 2-TFP-COF@PNFs CPEs exhibit a high room-temperature ionic conductivity of 1.68 × 10 S cm along with ultra-stable Li||Li symmetric cell cycling exceeding 8500 h. Interestingly, the well-designed CPEs are highly compatible with layered oxides and polyanion compounds; especially, the Li|2-TFP-COF@PNFs|LiFePO full cells deliver a higher initial discharge capacity of 106 mAh g at 10 C with long-term cycling stability after 4000 cycles as well as excellent wide-temperature adaptability (-40°C to 60°C) and compatibility with high mass loadings. Impressively, the assembled pouch cells realize stable cycling for 100 cycles. This work efficiently addresses the core issues of unstable SEI layers and low ionic transport efficiency, offering a highly promising strategy for designing high-performance SSLMBs.
Tian J, Yang Z, Xiao T
… +7 more, Su Z, Li T, Li J, Song Y, Shi K, Shan L, Liu Q
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374908
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Lithium-sulfur (Li-S) batteries are attractive for next-generation energy storage, yet practical deployment is impeded by the lithium polysulfides (LiPSs) shuttle effect and sluggish sulfur redox kinetics, which are furt...Lithium-sulfur (Li-S) batteries are attractive for next-generation energy storage, yet practical deployment is impeded by the lithium polysulfides (LiPSs) shuttle effect and sluggish sulfur redox kinetics, which are further aggravated by solvent shielding that blocks LiPSs from accessing catalytic sites. Here, we develop a yolk-shell MoO/CoO@C nanoreactor that leverages oxygen bridge-induced orbital oscillation to break the solvation barrier and accelerate interfacial conversion. We identify that the dynamic vibration of Mo-O-Co oxygen bridges facilitates a directional electron flow via a 4d-2p-3d orbital interaction pathway, which fundamentally triggers a low-spin to high-spin transition of Co centers, strengthening d-p orbital hybridization and enabling robust chemisorption/catalysis of LiPSs. Meanwhile, the modulation of solvation structure from solvent-separated ion pairs (SSIPs) to contact ion pairs (CIPs)/aggregates (AGGs) lowers the Li desolvation energy barrier and homogenizes the ion flux. Synergistically, the double-shelled architecture confines soluble intermediates and suppresses outward diffusion. Consequently, Li-S batteries deliver 352 mAh g at an ultrahigh rate of 15 C, and an initial areal capacity of 11.95 mAh cm is achieved at an ultrahigh sulfur loading of 13.03 mg cm. This work proposes a strategy of oxygen-bridge-induced high-spin state to realize desolvation and mass-transfer reaction of LiPSs within interface catalytic domain.
Wang D, Zhao G, He Y
… +7 more, Wang F, Zhang Y, Wei S, Jia Z, Zhao X, Wang P, Loh TP
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374907
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Transition-metal-catalyzed dicarbofunctionalization of alkenes represents a powerful strategy for building molecular complexity in a single step. Here we report an unprecedented nickel-catalyzed 1,2-arylalkenylation of u...Transition-metal-catalyzed dicarbofunctionalization of alkenes represents a powerful strategy for building molecular complexity in a single step. Here we report an unprecedented nickel-catalyzed 1,2-arylalkenylation of unactivated alkenyl alcohols using alkenyl boronates and aryl iodides. This method uniquely leverages the native hydroxyl group as an intrinsic directing handle, eliminating the need for pre-installed auxiliaries and streamlining the synthesis of structurally diverse alkenol derivatives. The reaction proceeds under mild conditions with broad functional group tolerance and excellent regioselectivity, enabling efficient construction of valuable building blocks. Mechanistic studies, supported by DFT calculations, reveal a Ni(0)/Ni(I)/Ni(II) catalytic cycle probably involving aryl radical intermediates. By exploiting alcohols as directing groups, this work expands the scope of alkene dicarbofunctionalization and provides a versatile platform for late-stage functionalization relevant to pharmaceuticals, agrochemicals, and materials development.
Cui S, Tian J, Zhu M
… +13 more, Liu Z, Cao Y, Liu Y, Feng Y, Xu W, Lai W, Yang H, Xu J, Guo B, Qiu L, Yang Z, Falcaro P, Ge J
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374906
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Controlling biocatalytic activity in melt-processed polymers is a central challenge for triggered depolymerization, because enzymes deactivate at melt-extrusion temperatures. Here, metal-organic framework-gated biocataly...Controlling biocatalytic activity in melt-processed polymers is a central challenge for triggered depolymerization, because enzymes deactivate at melt-extrusion temperatures. Here, metal-organic framework-gated biocatalysis, achieved by encapsulating enzymes within zeolitic imidazolate framework-8 (ZIF-8), preserves > 85% activity after 2 min at 180°C while regulating substrate access. Enzyme@ZIF-8 biocomposite production scales to ∼50 kg day and is compounded by twin-screw extrusion into poly(ε-caprolactone) (PCL), poly(butylene adipate-co-terephthalate) (PBAT), and polylactide (PLA) at a tonne-per-day scale; pellets are compatible with standard thermoforming. The enzyme@ZIF/plastic composites retain mechanical performance comparable to the neat polymers during processing and use. At the end-of-life, chemical triggers dissolve the ZIF-8 gate, releasing the enzyme, Zn and imidazolate to cooperatively accelerate depolymerization. Degradation increases 13.3-62.8-fold for PCL and PLA in water and 1.7-fold under industrial composting for PBAT and enables anaerobic PBAT digestion, whereas pristine polyesters show negligible conversion. This melt-processable platform establishes gated, on-demand depolymerization compatible with industrial polymer manufacturing.
Zhao X, Tang D, Gong C
… +3 more, Lei K, Fang R, Li Y
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374897
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Here, we report a one-pot tandem catalytic system that integrates CO hydrogenation to CHO* intermediates with their in situ esterification using dicarboxylic acids, directly yielding dimethyl esters (e.g., polyester mono...Here, we report a one-pot tandem catalytic system that integrates CO hydrogenation to CHO* intermediates with their in situ esterification using dicarboxylic acids, directly yielding dimethyl esters (e.g., polyester monomers for polyethylene terephthalate (PET) manufacturing) as final products with >99% selectivity. This system is enabled by a metal-organic framework (MOF)-derived catalyst featuring carbon-nanoconfined atomic Cu sites anchored on ca. 1.8 nm tetragonal ZrO nanoparticles (Cu-ZrO-C), which achieves an efficient CO conversion of 28% at a reduced temperature of 150°C in a batch reactor. The process delivers a high space-time yield of esters, corresponding to a CO conversion efficiency of 158.6 g g h. Mechanistic studies gained from control experiments, in situ time-resolved diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and density functional theory (DFT) calculations reveal that a tripartite synergy among atomic Cu sites, oxygen vacancies, and surface hydroxyls on t-ZrO nanoparticles stabilizes key intermediates (*CO, *COOH, *HCOO, *CHO) and opens a hydroxyl mediated pathway. This pathway redirects the typically poisoning *CO species toward *CHO, thereby circumventing the persistent *CO poisoning challenge. This work presents an atomic-level design strategy that simultaneously advances low-temperature CO hydrogenation and intermediate valorization, establishing an integrated and carbon-efficient route from CO to polymer feedstocks.
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374896
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Cage structure prediction has made significant strides by generating structures based on what the community has seen before. However, to computationally design and discover novel structures, the community must be able to...Cage structure prediction has made significant strides by generating structures based on what the community has seen before. However, to computationally design and discover novel structures, the community must be able to evaluate and model all structural candidates. Here, we introduce unbiased structure prediction workflows in our software, cgx, facilitated by exploration algorithms and our low-cost minimal models. By comparing to experiments, we show that our approach predicts cage structures starting only from the experimental inputs (building block types, features and their stoichiometry). We demonstrate the use of this method prior to any costly experimental commitment, providing an efficient automated approach that is open source and applicable to multiple model resolutions. By providing recipes with copyable code in the documentation, we make uptake of this new method as facile as possible for chemists with a wide-range of expertise.
Fu JL, Wu JY, Fan Q
… +3 more, Xue JH, Li Q, Wang H
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374891
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Alkyl-substituted internal alkynes are useful motifs in organic synthesis and medicinal chemistry, but their preparation from common amine precursors remains challenging. Aliphatic primary amines are widespread functiona...Alkyl-substituted internal alkynes are useful motifs in organic synthesis and medicinal chemistry, but their preparation from common amine precursors remains challenging. Aliphatic primary amines are widespread functional groups, yet their direct use as alkylating reagents is limited by the strength of the C(sp)─N bond. Herein, we describe a direct deaminative alkynylation of aliphatic primary amines using alkynyl bromides as coupling partners. The transformation proceeds under metal-free conditions with an N-anomeric amide as a nitrogen-deletion reagent, enabling formation of C(sp)─C(sp) bonds without prior amine prefunctionalization. The reaction shows good functional-group tolerance and accommodates a range of aliphatic amines, including substrates derived from pharmaceuticals and natural products. This study demonstrates the feasibility of converting aliphatic primary amines into internal alkynes and expands the scope of deaminative C─C bond-forming reactions.
Ye W, Li Y, Jing S
… +7 more, Wang C, Yan Y, Yang S, Xue Q, Li Y, Li X, Lai WY
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374887
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The development of dynamic organic phosphorescent polymers is often limited by the challenge of exerting precise and reversible control over their condensed matter structures. While external stimuli can modulate emission...The development of dynamic organic phosphorescent polymers is often limited by the challenge of exerting precise and reversible control over their condensed matter structures. While external stimuli can modulate emission, a fundamental materials-level principle for governing hierarchical reorganization remains elusive. Here, we report that ion-driving entanglement of polymer chains serves as a powerful general strategy to direct reconfigurable hierarchical structures, thereby enabling highly tunable organic phosphorescence. Specifically, potassium ions programmatically bridge ether and sulfonic acid groups within κ-carrageenan (κCG), triggering polymer entanglement and chromophore aggregation to form a dynamically reversible architecture. This structural transformation, validated by atomic force microscopy (AFM) and rheology, grants control over triplet exciton behavior, yielding phosphorescence that is tunable from blue to green (CIEy: 0.037-0.382) with a lifetime of up to 199.50 ms and an efficiency of 17.97%. The entanglement is thermally reversible, allowing on-demand emission switching. Furthermore, we demonstrate the translational potential of this mechanism by constructing a visual urinary potassium analyzer, where ion-concentration-dependent phosphorescence enables quantitative detection. This work establishes polymer entanglement as a central design principle for adaptive photonic materials, opening avenues for smart sensing and healthcare monitoring.
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374880
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We report the synthesis and the characterization of a multicomponent molecular machine based on a [3]rotaxane architecture. The system is composed by two crown ether macrocycles and an axle with three recognition sites f...We report the synthesis and the characterization of a multicomponent molecular machine based on a [3]rotaxane architecture. The system is composed by two crown ether macrocycles and an axle with three recognition sites for the rings: ammonium (AmH), bipyridinium (Bpy), and triazolium (Trz). The position of the two rings can be precisely controlled via a sequence of chemical and electrochemical inputs: the two rings can be located on neighboring stations, forced on the same station or separated at the opposite extremities of the axle. This complex mechanism is elucidated by a combination of NMR spectroscopy and voltammetric techniques, allowing to characterize the thermodynamics of the reaction network. The investigation shows that each ring is influenced by the presence and position of the other, resulting in a coupled motion, a critical feature for the development of next-generation molecular machines.
Charvillat T, Bernardelli P, Daumas M
… +5 more, Pannecoucke X, Ferey V, Oulyadi H, Sebban M, Besset T
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374876
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A robust method for the hydrogenation of various pyridines substituted by CF, CFH, and CFCOEt groups has been developed. Using an inexpensive heterogeneous Pd/C catalyst, diversely functionalized fluorinated piperidines...A robust method for the hydrogenation of various pyridines substituted by CF, CFH, and CFCOEt groups has been developed. Using an inexpensive heterogeneous Pd/C catalyst, diversely functionalized fluorinated piperidines were synthesized under air- and moisture-tolerant reaction conditions (37 examples, up to 98% yield) with good to high diastereoselectivity. Comprehensive NMR studies enabled full structural characterization of the synthesized fluorinated compounds. The synthetic utility of the methods was further highlighted by the gram-scale preparation of the fluorinated scaffolds and the synthesis of a trifluoromethylated analog of the antipsychotic drug melperone.
Wang C, Nallathambi V, Wang L
… +8 more, Kresse J, Shkodich NF, Farle M, Hübner R, Eychmüller A, Reichenberger S, Barcikowski S, Cai B
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374872
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Publisher ↗
Electrosynthesis of HO is attractive for its environmental sustainability and cost-effectiveness, yet is impeded by the sluggish reaction kinetics and low selectivity triggered by the competing 4e pathway. Here, a model...Electrosynthesis of HO is attractive for its environmental sustainability and cost-effectiveness, yet is impeded by the sluggish reaction kinetics and low selectivity triggered by the competing 4e pathway. Here, a model transition-metal-based multimetallic aerogel was designed using CrMnFeCoNi HEA nanoparticles from nanosecond-pulsed laser synthesis in liquids, along with three exemplary quaternary systems without Co, Fe, and Ni, respectively. Among them, the resulting CrMnFeCoNi HEA aerogel exhibits the highest HO selectivity of 95% and the lowest transferred electron number of 2.1, as well as good stability of nearly 100% HO selectivity after 10k cycles. Furthermore, the as-prepared CrMnFeCoNi aerogel reaches a maximum HO yield of 2.34 mmol h and demonstrates an efficient decolorization ability for organic pollutants (e.g., Methylene blue or Rhodamine B). This outstanding performance is attributed to the synergetic effects of the various metals and the configurational entropy contribution, enabling a favored distribution of surface atom arrangements and optimal binding energies during electrochemical reactions. This work not only provides a novel perspective for manipulating HEA aerogels but also presents a promising alternative for industrial HO production and water treatment.
Dai J, Zhang Z, Wang W
… +4 more, Ding M, Pan F, Zhang J, Tian H
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374867
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Biological systems regulate photochemical functions through transient activation states that determine when a stimulus can produce a response. Inspired by this principle, we develop a temporally gated molecular platform...Biological systems regulate photochemical functions through transient activation states that determine when a stimulus can produce a response. Inspired by this principle, we develop a temporally gated molecular platform in which dynamic pH evolution controls visible-light photochemistry. The system integrates a proton-responsive charge-transfer complex (CTC) sensitizer and a diarylethene photoswitch. Reversible protonation of the CTC enables chemical gating of triplet-sensitized photochromism, which further generates a transient activation window via coupling with a dissipative, pH-regulation network. As a result, identical optical stimuli lead to distinct outcomes depending on when they are applied during chemical evolution, effectively promoting chemical gating to temporal gating of molecular photoswitch. The progressive modulation of the sensitizer induces a time-dependent attenuation of photochemical responses, enabling adaptive behaviors reminiscent of visual fatigue in biological photo-reception.
Yan Y, Ma J, Zhang W
… +10 more, Tang H, Li Y, Mei R, Huang Y, Karnaushenko D, Karnaushenko DD, Luo Y, Zhang K, Schmidt OG, Zhu M
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42374862
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Publisher ↗
Ion transport at electrified interfaces is conventionally described by the redistribution of mobile ions to preserve local electroneutrality. Under extreme electrolyte confinement, however, this assumption fails as the c...Ion transport at electrified interfaces is conventionally described by the redistribution of mobile ions to preserve local electroneutrality. Under extreme electrolyte confinement, however, this assumption fails as the characteristic transport length approaches the Debye screening length, giving rise to space-charge accumulation and slow electrostatic relaxation that dominate interfacial kinetics. Here, we introduce a fixed-charge-selective interphase in which immobile anionic charges replace mobile electrolyte anions as the primary charge-compensating species, thereby establishing a chemically encoded electrostatic boundary condition. Using a glucose-derived network as a model system, we show that localized fixed charge enables cation-selective transport and suppresses extended space-charge layers (ESCLs) by eliminating the slow relaxation pathways. Spatiotemporal transport analysis reveals that this interphase collapses multi-timescale interfacial relaxation into a unified kinetic regime. When applied to nanoliter-confined electrochemical systems (45 nL), rest-induced Coulombic efficiency (CE) collapse is reduced from 40% to 5%, demonstrating stabilization of electrostatic relaxation during idle periods, which is a failure mode intrinsic to microscale devices operating under duty cycles. The concept is further validated under pH-coupled and oxidative-stress conditions, sustaining stable operation with strong rate capability. These results define a general chemical strategy for regulating interfacial ion transport under confinement by replacing mobile charge compensation with molecularly fixed charges.
You S, Yang C, Shuai X
… +10 more, Xu J, Zhang Y, Huang B, Liu G, Kim HH, Woo HY, Kuang Z, Wu F, Liu J, Chen L
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42360836
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Publisher ↗
Back-to-back dimeric acceptors have attracted widespread attention for organic solar cells (OSCs) due to their exceptional stability and unique three-dimensional (3D) charge transport channels. However, these dimers suff...Back-to-back dimeric acceptors have attracted widespread attention for organic solar cells (OSCs) due to their exceptional stability and unique three-dimensional (3D) charge transport channels. However, these dimers suffer from inferior intermolecular interactions and molecular packing, limiting the development of OSCs. Here, we first employed an asymmetry end-group strategy to develop a novel asymmetry back-to-back dimer DQx-FCl. Breaking structural symmetry in DQx-FCl alters the electrostatic surface potential to strengthen intermolecular π-π interactions. Meanwhile, it also reduces the overlap of electron and hole in the singlet excited state to promote charge separation. Thus, the asymmetric DQx-FCl-based binary device achieved a superior power conversion efficiency (PCE) of 19.11% along with improved stability, relative to its symmetric DQx-F. More notably, DQx-FCl-based ternary device achieves a record PCE of 20.27% among reported back-to-back dimer-based OSCs. Furthermore, the reinforced intermolecular interactions also enhance the mechanical robustness of OSCs. Flexible devices based on the PM6:L8-BO:DQx-FCl attain a PCE of 17.27% with a crack-onset strain of 14.6%, while the intrinsically stretchable OSC retains 80% of its initial efficiency under a tensile strain exceeding 23%. This study demonstrates the great potential of asymmetric back-to-back dimeric acceptors for improving efficiency, stability, and mechanical flexibility toward high-performance OSCs.
Zhang X, Wang Y, Jiao H
… +4 more, He Y, Li H, Zhang J, Bu XH
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42360833
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Aiming at the core challenges in MOF photocatalysts-severe bulk charge recombination and insufficient surface active sites-this study innovatively proposes an interfacial D-A (Donor-Acceptor) system. Through a self-optim...Aiming at the core challenges in MOF photocatalysts-severe bulk charge recombination and insufficient surface active sites-this study innovatively proposes an interfacial D-A (Donor-Acceptor) system. Through a self-optimized process of nanoconfinement, irradiation decomposition, recapture, and redistribution, three PtL acceptors with different coordination environments, anchored on NH-MIL-125 via amide bonds like antennas, not only undergo self-excitation under light irradiation but also act as electron acceptors to capture and converge the electrons supplied by the MOF host. Furthermore, the precise tuning of the Pt-N ← Pt-N → Pt-S coordination microenvironment was achieved, and the optimized d-band center of Pt-S effectively balances the activation of water molecules and the transformation kinetics of hydrogen intermediates. Ultimately, NML-Ptbtp achieves a high hydrogen evolution rate of 901.7 mmol g h and an apparent quantum yield of 14.5% at 365 nm. This work proposes the concept of an interfacial D-A system for the first time and, through in situ experiments combined with theoretical simulations, confirms its self-excited reaction behavior and electron-acceptor-induced bifunctionality, thereby revealing a novel optimization mechanism for photogenerated charge separation and surface reaction processes.
Li X, Xiang J, Cui H
… +10 more, Qin L, Xu Y, Chen L, Tressel J, Wang M, Zhou H, Feng Z, Qiu X, Chen S, Chen S
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42360813
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Publisher ↗
Oxygen reduction reaction (ORR) represents a critical process in advanced electrochemical energy technologies. Yet, the fundamental mechanism of ORR selectivity has remained largely elusive. Herein, electron spin state i...Oxygen reduction reaction (ORR) represents a critical process in advanced electrochemical energy technologies. Yet, the fundamental mechanism of ORR selectivity has remained largely elusive. Herein, electron spin state is identified as the underlying factor governing ORR selectivity for hydrogen peroxide (HO) production using model-definite and site-identical molecular catalysts as testing platforms. Experimentally, a series of cobalt phthalocyanine (CoPc) derivatives are synthesized, and an explicit correlation is found between the Co spin state and ORR selectivity, where HO production increases with elevated spin states. Combined theoretical orbital analysis and in situ spectroscopy investigations unveil that the spin state transition and subtle d-orbital rearrangements optimize multiple orbital hybridization with key intermediates and facilitate the selective two-electron ORR. Among the series, tetra-hydroxyl modified CoPc with a high spin state achieves a two-electron ORR performance in neutral media superior to those of low-spin state CoPc and previously reported catalysts, with HO selectivity over 95% within the potential range of +0.1 to +0.42 V and a remarkable HO yield of 191.22 mg cm h at -350 mA cm. These findings advance the fundamental understanding of the electronic structure effect on catalytic behaviors.