Liu N, Gong Y, Li S
… +5 more, Xing R, Ni Y, Qin B, Li F, Wang L
Angew Chem Int Ed Engl
· 2026 Jul · PMID 42390834
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Organic electrode materials often face challenges of low electronic conductivity and high solubility in electrolytes. To address this, we synthesized Cu-DHAQ, a layered metal-organic coordination polymer using 1,4-dihydr...Organic electrode materials often face challenges of low electronic conductivity and high solubility in electrolytes. To address this, we synthesized Cu-DHAQ, a layered metal-organic coordination polymer using 1,4-dihydroxyanthraquinone (DHAQ) as the ligand and Cu as the metal center. Coordination polymerization effectively suppresses DHAQ dissolution and enhances cycling stability. The extended π-conjugated framework promotes charge delocalization, improving conductivity, while the layered structure facilitates Li diffusion. Cu-DHAQ features dual redox-active centers (Cu/Cu and C═O/C─O), enabling a three-electron transfer reaction. Benefiting from these synergistic effects, the Cu-DHAQ cathode delivers a high discharge capacity of 260.5 mAh g with 81.2% retention after 100 cycles, and maintains 119.4 mAh g at 0.5 A g. Furthermore, both coin and pouch full cells using Cu-DHAQ cathode and pre-lithiated hard carbon (Li-HC) anode were successfully demonstrated, highlighting its potential as a high-performance organic cathode material for lithium batteries.
Jiang Y, He X, Zhang X
… +4 more, Dan W, Chen Z, Zhang C, Fei H
Angew Chem Int Ed Engl
· 2026 Jul · PMID 42390832
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Bimetallic alloy nanoclusters provide an ideal platform for photocatalytic CO reduction owing to their synergistic, charge-polarized electronic effects that facilitate C─C coupling. However, their application is hindered...Bimetallic alloy nanoclusters provide an ideal platform for photocatalytic CO reduction owing to their synergistic, charge-polarized electronic effects that facilitate C─C coupling. However, their application is hindered by three major challenges: poor stability associated with their ultrasmall size, difficulty in precise multi-metal composition control, and the lack of universal ligand-anchoring strategies. Herein, we report the first family of covalently stabilized, composition-tunable AuCu alloy nanoclusters confined within an N-heterocyclic carbene (NHC)-functionalized metal-organic framework (MOF, UiO-68-NHC-AuCu, 4 ≤ x ≤ 10) via robust metal-NHC covalent bonds. The porous framework spatially confines ∼2 nm alloy nanoclusters to prevent aggregation while enabling precise modulation of the Au:Cu composition. Among the series, UiO-68-NHC-AuCu exhibits the highest photocatalytic performance, achieving a C hydrocarbon evolution rate of 42.5 µmol g h with a C selectivity of 77% (electron-based), outperforming the vast majority of MOF/metal heterojunction and metal nanocluster-based photocatalysts. In situ spectroscopic investigations and computational studies reveal that the synergistic Au─Cu sites promote C─C coupling via the formation of *COCOH intermediates, a pathway that is thermodynamically unfavorable over monometallic Au─Au sites. This work establishes a robust strategy for constructing MOF-confined bimetallic nanoclusters with synergistic active sites, achieving efficient and selective CO photoreduction to high-value multi-carbon products.
Cerrón-Calle GA, Arias-Sanchez AN, Flores M
… +3 more, Roldan MA, Sánchez-Sánchez CM, Garcia-Segura S
Angew Chem Int Ed Engl
· 2026 Jul · PMID 42390830
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The electrochemical reduction of nitrate (ERN) to ammonia (NH) has attracted increasing attention as a sustainable route for nitrogen recovery and green ammonia production, enabled by major advances in electrocatalyst de...The electrochemical reduction of nitrate (ERN) to ammonia (NH) has attracted increasing attention as a sustainable route for nitrogen recovery and green ammonia production, enabled by major advances in electrocatalyst design over the past decade. Two mechanistic pathways are generally well-recognized: direct electron transfer and a hydrogen radical (H*)-mediated mechanism. However, the latter remains difficult to quantify under practical electrochemical conditions, limiting mechanistic comparison across catalyst configurations. Herein, Ni/Co, Ni/Pt, and Ni/Pt/Co electrocatalysts were investigated to elucidate the interplay between direct and indirect ERN pathways. Quantitative electron spin resonance (ESR) measurements of H* under ERN-relevant conditions, combined with bulk electrolysis in the absence and presence of an H* scavenger, enabled direct correlation between H* availability and NH production. Ni/Co predominantly follows direct electron transfer, whereas Ni/Pt transitions to an H*-mediated regime above a threshold current density. In contrast, Ni/Pt/Co exhibits synergistic behavior in which both pathways coexist. Moreover, the H* role varies with electrocatalyst chemical composition, facilitating either NO activation or NO hydrogenation. These findings establish a quantitative framework for resolving H*-mediated contribution in ERN and provide mechanistic design principles applicable to other electrocatalytic hydrogenation reactions.
Angew Chem Int Ed Engl
· 2026 Jul · PMID 42390823
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Photodynamic therapy (PDT) is a non-invasive modality for cancer treatment, but its broader application remains constrained by two central limitations, that is, insufficient tissue penetration of excitation light and the...Photodynamic therapy (PDT) is a non-invasive modality for cancer treatment, but its broader application remains constrained by two central limitations, that is, insufficient tissue penetration of excitation light and the limited performance of available photosensitizers (PSs). Two-photon PDT (TP-PDT) offers a powerful strategy by enabling near-infrared excitation with deeper penetration, higher spatial precision, and reduced off-target photodamage. In this context, metal complexes have emerged as particularly attractive TP PSs because their coordination frameworks allow precise control over spin-orbit coupling, excited-state dynamics, redox reactivity, and reactive oxygen species generation through both Type I and Type II pathways. Recent advances show that ligand engineering, photo-decaging strategies, supramolecular design, and nanostructuring can substantially enhance two-photon absorption, charge separation, radical generation, and therapeutic efficacy, especially in hypoxic tumors. This review overviews recent progress in two-photon-activatable metal complexes for PDT, highlighting design principles and therapeutic advances across ruthenium-, iridium-, platinum-, and related metal-based complexes. Particular emphasis is given to how coordination design governs photophysical properties, biological performance, and treatment outcomes. Current challenges and future opportunities for the clinical translation of these systems are also discussed.
Huang T, Han J, Lu B
… +3 more, Wu Y, Zhang Y, Liu S
Angew Chem Int Ed Engl
· 2026 Jul · PMID 42390814
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Photocatalytic CO reduction to valuable multicarbon products like ethanol is a promising strategy for solar energy conversion, yet remains challenged by kinetically constrained C-C coupling and competitive C-O cleavage t...Photocatalytic CO reduction to valuable multicarbon products like ethanol is a promising strategy for solar energy conversion, yet remains challenged by kinetically constrained C-C coupling and competitive C-O cleavage toward ethylene. Herein, an electrophile-nucleophile pairing strategy is developed by constructing atomically Cu-Zr heteronuclear dual sites within a porphyrinic framework, which can simultaneously reduce repulsion for C-C coupling and strengthen the C-O bond. The electron-deficient Zr, as a strong oxygen-affixed anchor, stabilizes critical *OCH intermediates via O-coordination, while adjacent electron-rich Cu sites drive *CO adsorption-inducing charge asymmetry between *OCH and *CO for kinetically favored dimerization. Subsequent hydrogenation selectively proceeds toward ethanol due to enhanced Zr-O stabilization that prevents C-O scission. The optimized catalyst achieved a near-unity ethanol selectivity at 87.8 µmol·g·h using water as a scavenger under a CO pressure of 0.5 MPa, which further increased to 195.1 µmol·g·h at 1.5 MPa. This work establishes mismatched electrophile-nucleophile pairs as a versatile design principle for steering photocatalytic CO reduction toward value-added multicarbon products.
Xian W, Si Y, Yang F
… +9 more, Chen Z, Ji X, Dai Z, Song C, Cheng Y, Liu B, Li B, Wu G, He D
Angew Chem Int Ed Engl
· 2026 Jul · PMID 42390794
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Artificial ion nanochannels enabling precise discrimination between monovalent and multivalent cations are essential for resource recovery and ion separation. However, due to the inadequate differentiation of their trans...Artificial ion nanochannels enabling precise discrimination between monovalent and multivalent cations are essential for resource recovery and ion separation. However, due to the inadequate differentiation of their transmembrane energy barriers, these nanochannels still face challenges in achieving high permeability alongside high selectivity. Herein, we report that a trisodium citrate-mediated MXene laminar membranes (MLM-CA-3Na) possess highly permeable and selective Li/Ca separation. As confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption spectroscopy, the uniform stacking of the citrate ligand/Na synergistically modified MXene monolayer nanosheets has achieved highly ordered confined subnanochannels of MLM-CA-3Na membranes. Molecular dynamics simulations, potential of mean force calculations, and transport energy barrier analysis revealed that the confined subnanochannels of MLM-CA-3Na membranes efficiently regulate the dehydration and transport behaviors of Li and Ca, leading to a pronounced differentiation in their transmembrane energy barriers. The obtained MLM-CA-3Na membranes exhibited a Li permeation rate of 0.0725 mol m h, a Li/ Ca selectivity of 84, and long-term durability over 100 h. This work identifies ligand-cation interactions as key regulators for ion separation, providing a design paradigm for sustainable lithium extraction.
Shi TH, Geng X, Tuo DH
… +7 more, Mizuno M, Tanaka Y, Seki T, Ohtani S, Kato K, Okuno S, Ogoshi T
Angew Chem Int Ed Engl
· 2026 Jul · PMID 42390773
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Introducing mechanical interlocking into epoxy thermosets can enhance material performance. However, this method typically requires complex monomer design and elaborate synthesis. Here, we demonstrate a simple strategy t...Introducing mechanical interlocking into epoxy thermosets can enhance material performance. However, this method typically requires complex monomer design and elaborate synthesis. Here, we demonstrate a simple strategy that exploits the dual functionality of a commercially available hydroxylated pillar[5]arene, which acts simultaneously as a macrocyclic host and a rigid cross-linking unit. By threading polymer chains through the macrocycles, poly(pseudo)rotaxanes consisting of rigid wheels and flexible axles were formed. Then, in situ curing fixed the pillar[5]arene into the epoxy networks through both mechanical and covalent bonding. The resulting materials exhibited a balanced combination with tensile strength of 29.7 MPa and toughness of 21.6 MJ·m. This approach enabled fine-tuning of the mechanical properties of the epoxy networks by varying the pillar[5]arene content and epoxy precursor lengths. By combining supramolecular threading with covalent network formation using a single macrocycle, this work provides a convenient and practical route to regulating epoxy network properties.
Yan D, Song W, Zhao Z
… +6 more, Ding Y, Jiang Z, Qi Q, Ge Z, Wang Y, Liu Y
Angew Chem Int Ed Engl
· 2026 Jul · PMID 42390768
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The advancement of high-performance n-type organic mixed ionic-electronic conductors (OMIECs) is pivotal to advancing organic electrochemical transistors (OECTs) for next-generation bioelectronics. While current design s...The advancement of high-performance n-type organic mixed ionic-electronic conductors (OMIECs) is pivotal to advancing organic electrochemical transistors (OECTs) for next-generation bioelectronics. While current design strategies predominantly center on non-ionic conjugated polymers, their inherently hydrophobic backbones lead to suboptimal ionic transport characteristics. To address this challenge, we introduce an ionic acceptor design strategy of backbone cationization via B ← N functionalization within bipyridine and bipyrazine frameworks. Leveraging these cationic acceptors, we synthesized two n-type ionic polymer OMIECs, PBPyBF, and PBPzBF, which exhibit low-lying LUMO levels as low as -4.0 eV, elevated backbone torsional barriers, and ordered microstructures. Most critically, backbone cationization via B ← N coordination significantly enhances hydrophilicity by inducing a distinct porous film morphology, facilitated by hydrogen bonding with processing solvents. This structural evolution translates to a dramatically improved volumetric capacitance of 581 F cm. Consequently, OECTs based on cationic polymer PBPzBF exhibit an exceptional normalized transconductance of 38.9 S cm and figure of merit of 215.9 F cm V s, ranking among the highest values reported for n-type OMIECs to date. Notably, electrocardiogram sensors integrated with PBPzBF-OECTs exhibit high signal-to-noise ratios and superior sensitivity. This work establishes fundamental structure-property relationships governing ion-electron coupled transport in conjugated polymers.
Angew Chem Int Ed Engl
· 2026 Jul · PMID 42390755
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"Chemistry is fun because, by combining simple building blocks, one can create increasingly complex molecules… My favorite name reaction is the Sonogashira cross-coupling…" Find out more about Zulema Fernández in her Int..."Chemistry is fun because, by combining simple building blocks, one can create increasingly complex molecules… My favorite name reaction is the Sonogashira cross-coupling…" Find out more about Zulema Fernández in her Introducing… Profile.
Li W, Liu J, Guo J
… +8 more, Song A, Chen S, Chen R, Zhong Y, Xing Y, Sun J, Tian Z, He G
Angew Chem Int Ed Engl
· 2026 Jul · PMID 42390712
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Aqueous zinc-ion batteries (AZIBs) are promising for large-scale energy storage due to environmental friendliness, inherent safety, and low cost. However, the practical deployment of AZIBs is hindered by notorious side r...Aqueous zinc-ion batteries (AZIBs) are promising for large-scale energy storage due to environmental friendliness, inherent safety, and low cost. However, the practical deployment of AZIBs is hindered by notorious side reactions at the zinc (Zn) anode, which seriously deteriorate the battery stability and reversibility. Here, we propose guanidine sulfate (GS) as an electrolyte additive, leveraging a cation-anion synergistic mechanism to jointly inhibit side reactions. Both theoretical and experimental results confirm that the guanidine cation (CHN ) preferentially adsorbs on the Zn anode surface, providing an electrostatic shielding effect that promotes uniform Zn deposition. Concurrently, the sulfate anion (SO ) contributes to the formation of a robust solid electrolyte interface (SEI), effectively inhibiting dendrite growth and enhancing interfacial stability. Consequently, Zn||Cu asymmetric cells with GS deliver a high Coulombic efficiency of 99.6% over 1200 cycles, while Zn||Zn symmetric cells exhibit an extended lifespan exceeding 500 h at various current densities. Furthermore, the Zn||O-NVO·nHO full cells demonstrate outstanding cycling stability, retaining over 90% of initial capacity after 2000 cycles at current densities of 2 and 5 A g. This research provides a viable electrolyte design strategy leveraging cation-anion synergy, offering new insights into electrolyte modulation and advancing the performance of AZIBs.
Tan Y, Tian T, Chen H
… +6 more, Yang G, Yang M, Zhong JX, Chen ZR, He Y, Wu WQ
Angew Chem Int Ed Engl
· 2026 Jul · PMID 42390036
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Blue-emitting metal halide perovskites remain difficult to stabilize because mixed-halide compositions suffer from halide heterogeneity, defect formation, and rapid phase segregation. Here, we report a supramolecular hos...Blue-emitting metal halide perovskites remain difficult to stabilize because mixed-halide compositions suffer from halide heterogeneity, defect formation, and rapid phase segregation. Here, we report a supramolecular host engineering strategy that stabilizes mixed-halide perovskites using a quaternary ammonium chloride-functionalized cationic β-cyclodextrin (C-βCD). The cyclodextrin host simultaneously functions as a chlorine reservoir, defect passivator, and supramolecular stabilizer, enabling homogeneous halide incorporation and strong host-guest interactions with the CsPbBr-CsPbBr heterostructured perovskite surface. This cooperative regulation effectively suppresses halide segregation and non-radiative recombination, yielding tunable blue emission with exceptional color purity and a near-unity photoluminescence quantum yield (PLQY) of 99.9%, among the highest values reported for blue-emitting perovskites. The resulting supramolecular perovskite luminescent membranes further exhibit remarkable stability against water exposure (93.3% of initial PL intensity retained after 626 h) and ambient environmental stress (a PLQY half-life of 27457 h), establishing a new benchmark for environmentally robust blue emitters. Integration of the supramolecular perovskites within porous membranes enables multifunctional operation, including foldable display, white light-emitting diodes, as well as pioneer application of fluorescence detection and visible-light-driven degradation of perfluorinated pollutants. These results highlight supramolecular host-guest chemistry as a powerful molecular strategy for stabilizing mixed-halide perovskites and engineering robust luminescent materials.
He T, Zhang Z, Wu K
… +12 more, Li H, Gong Y, He X, Wu Y, Chen Y, Shi B, Yan W, Ma H, Li M, Ma M, Wang J, Yang H
Angew Chem Int Ed Engl
· 2026 Jul · PMID 42387254
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The electric double layer (EDL) governs local electrolyte enrichment and reduction pathways, thereby directing the nucleation and evolution of solid electrolyte interphase (SEI). However, electrolyte design is still larg...The electric double layer (EDL) governs local electrolyte enrichment and reduction pathways, thereby directing the nucleation and evolution of solid electrolyte interphase (SEI). However, electrolyte design is still largely guided by bulk solvation descriptors. Here, an asymmetric room temperature phosphonium ionic liquid, (2-methoxyethoxy)methyl phosphonium hexafluorophosphate (PMEP), is designed to promote an anion-reinforced EDL. Molecular asymmetry lowers the melting point of PMEP and promotes PF participation in Li-centered solvation structures. Molecular dynamics (MD) simulations and density functional theory (DFT) calculations suggest that PF can participate in Li-centered interfacial solvation clusters under selected charge states, which contributes to the formation of an SEI containing both organic reduction products and inorganic species such as LiF and LiO. This organic/inorganic SEI structure lowers interfacial impedance and the apparent activation barrier for Li transfer, enabling more uniform lithium deposition and a mechanically robust interface. Li|LiFePO batteries with an areal loading of 11.3 mg cm deliver 94.9% capacity retention after 600 cycles. The fabricated 1.6 Ah Graphite|LiFePO cylindrical cell operates stably for over 500 cycles with a Coulombic efficiency above 99.8%. This work demonstrates a shift in electrolyte design from bulk formulations toward interfacial solvation structure engineering for next generation batteries.
Liu S, Zhang Z, Seligmann B
… +4 more, Bui VH, Nguyen TM, Dang TT, Franke J
Angew Chem Int Ed Engl
· 2026 Jul · PMID 42387091
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The plant alkaloid camptothecin is a high-value precursor for the semi-synthesis of multiple anticancer drugs. The key transformation during its biosynthetic pathway is a yet enigmatic skeletal reorganization from a 6/5/...The plant alkaloid camptothecin is a high-value precursor for the semi-synthesis of multiple anticancer drugs. The key transformation during its biosynthetic pathway is a yet enigmatic skeletal reorganization from a 6/5/6 tetrahydro-β-carboline ring system to the 6/6/5 pyrroloquinoline scaffold, which is characteristic of camptothecin-related alkaloids. Here, we show that this scaffold transition can be efficiently catalyzed by flavin cofactors such as flavin mononucleotide in a photooxidative process. As part of this complex transformation, we verified the existence of a previously postulated macrocyclic ketolactam intermediate. Based on the mild conditions-oxygen, light, and flavins-we show that this conversion can also take place in leaves of Nicotiana benthamiana, a plant which does not normally produce camptothecin or related alkaloids. Our optimized biomimetic photochemical reaction conditions enable a short, mild, and efficient semi-synthesis of the alkaloids (3S)-pumiloside, (3R)-pumiloside, and vincosamide ketolactam, also known as turpiniside, without any protecting groups. Thus, our work improves our understanding of this key skeletal reorganization step forming the camptothecin scaffold in nature and provides streamlined photocatalytic access to camptothecin-related alkaloids.
Yin D, Yuan J, Lin D
… +10 more, Zhang Z, Fang W, Liu Z, Yang C, Duan X, Zheng A, Chen D, Zhou X, Wang L, Feng X
Angew Chem Int Ed Engl
· 2026 Jul · PMID 42386692
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The efficiency of tandem catalysis is fundamentally limited by the transport of transient intermediates. In the direct epoxidation of alkenes with H and O, in situ generated HO rapidly decomposes during diffusion, render...The efficiency of tandem catalysis is fundamentally limited by the transport of transient intermediates. In the direct epoxidation of alkenes with H and O, in situ generated HO rapidly decomposes during diffusion, rendering most Ti active sites kinetically inaccessible and imposing a long-standing performance ceiling. Here, we overcome this limitation by engineering hydrophobic transport channels via physical integration of a hydrophobic polymer with bifunctional Au/TS-1 catalysts. This microenvironment accelerates HO migration away from hydroxyl-rich surfaces toward remote Ti sites while suppressing nonproductive decomposition. Molecular dynamics simulation studies show that the diffusion of HO on hydrophobic surfaces is significantly higher than on hydrophilic surfaces, as reflected experimentally by a 25% increase in tandem HO efficiency. Moreover, the hydrophobic channels promote rapid desorption of epoxide products, suppressing ring-opening reactions and carbonaceous accumulation, resulting in a stable ∼90% epoxide selectivity over 200 h. This strategy exhibits broad generality across Au-Ti bifunctional catalysts for alkene epoxidation using in situ generated HO, with an outstanding H utilization efficiency of 73.5% achieved over the Au/TS-1-B catalyst under the identical standard reaction conditions employed throughout this work. This work establishes diffusion control of metastable surface species as a principle for breaking intrinsic transport-decomposition trade-offs in tandem catalysis.
Sun Y, Wu J, Zhou J
… +8 more, Xu D, He X, Dong X, Luo R, Liu R, Zhang K, Ma X, Wang B
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42378198
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Heterogeneous photocatalytic CO reduction provides a promising route for syngas production. However, high reaction energy barriers and inefficient charge separation and transfer hinder the surface CO reduction. Herein, o...Heterogeneous photocatalytic CO reduction provides a promising route for syngas production. However, high reaction energy barriers and inefficient charge separation and transfer hinder the surface CO reduction. Herein, on a covalent organic framework (COF) based catalyst, through the enhanced photoelectron transfer efficiency by introduction of N atoms, also the increased electron density of the Co (II) site with two negative one-valent bidentate ligands, we achieved both ultrahigh syngas production rate and high H/CO molar ratio. The best catalyst in this work: Triazine-COF-Co-SA enabled a record-high syngas production rate with high H/CO molar ratio (≥2) of 698.7 mmol g h. Femtosecond transient absorption spectroscopy (fs-TAS), in situ infrared spectroscopy (In situ IR) and theoretical calculation indicated that N introduction to the framework and active site electron density increasing were effective for the previous challenges. On Triazine-COF-Co-SA, the energy barrier was lowered from 1.90 to 0.54 eV, also fs-TAS showed an obvious τ = 1.5 ns which represented a higher charge transfer efficiency. This study shows great potential for catalyst modification on COF-based catalysts to enhance CO photoreduction capability.
Pal S, Maity D, Chakraborty J
… +5 more, Jha S, Sarma K, Koner N, Chakrabarty S, Das D
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42378156
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Metastable states are utilized by biology to power the construction of large and motile macromolecules and also to realize out-of-equilibrium phase separation. Energy transduction from orthogonal and unrelated exergonic...Metastable states are utilized by biology to power the construction of large and motile macromolecules and also to realize out-of-equilibrium phase separation. Energy transduction from orthogonal and unrelated exergonic reactions drives the contra-thermodynamic transformation, which acts as the catalyst for the exergonic reaction. Herein, we show that thermodynamically stable building blocks can undergo phase separation when the process is coupled with an exergonic degradation of their thermodynamically activated precursor. The thermodynamically stable products alone are incapable of accessing the droplets. The chemical transformation is critical to achieve pathway-controlled phase separation, which catalyzes the chemical transformation. The activated precursor undergoes a β-elimination reaction to produce an aromatic substrate along with trimethylammonium cations, which provide temporal stabilization to the phase-separated droplets. Droplet formation is not observed with precursors incapable of undergoing the β-elimination reaction. The generated droplets can imbibe diverse guest molecules, and their transition from droplets to proto-tissue-like structures is observed in the presence of porphyrin. Importantly, the kinetically accessed metastable liquid droplets are shown to augment the catalytic potential of hemin, cofactor of natural peroxidase, and accelerate the hydrolase-peroxidase cascade reaction.
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42378139
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Solid-state phase transitions provide a powerful platform for translating subtle molecular-level interactions into macroscopic functional responses; however, rational design strategies that enable predictable control ove...Solid-state phase transitions provide a powerful platform for translating subtle molecular-level interactions into macroscopic functional responses; however, rational design strategies that enable predictable control over such transitions remain limited. Herein, we report polymorphic structure-property switching behaviors associated with competing intermolecular interactions in luminescent molecular crystals. Cyano-β-substituted distyrylbenzene derivatives bearing bromo and methoxy side chains were designed to incorporate competing homotypic and heterotypic noncovalent interactions with distinct interaction characteristics. Single-crystal analyses reveal that subtle differences in the hierarchical ordering of dispersion-, dipole-dipole-, and electrostatically dominated interactions give rise to polymorphic crystal structures with distinct molecular orientations and photoluminescence properties. Thermal and mechanical stimuli induce distinct phase transitions: an irreversible thermally induced single-crystal-to-single-crystal transition and a pseudo-reversible mechanochemical pathway via an amorphous intermediate, both directly visualized as pronounced emission color changes. Kinetic and thermodynamic controls over polymorph formation are elucidated through a combination of structural analysis, photophysical measurements, and crystal framework calculations. This study suggests that multifunctional molecular side chains enable access to diverse interaction landscapes, allowing multiple structure-property switching pathways to be encoded within a single molecular framework. The presented framework provides a qualitative perspective for interpreting dynamic structural behaviors in molecular crystals.
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42376808
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Mixed metal oxides, such as ZnZrO, have attracted considerable interest as CO hydrogenation to methanol catalysts due to their high methanol selectivity (> 70%) and catalytic stability at elevated reaction temperatures (...Mixed metal oxides, such as ZnZrO, have attracted considerable interest as CO hydrogenation to methanol catalysts due to their high methanol selectivity (> 70%) and catalytic stability at elevated reaction temperatures (> 300°C). In this work, we introduce a novel ZnHfO catalyst that exceeds the intrinsic methanol formation rate of the reference ZnZrO at a Zn content of 20 mol% (r = 0.59 mol(molh), r = 0.68 mol(molh)). Remarkably and in contrast to ZnZrO, the ZnHfO-based catalysts exhibit a high methanol selectivity (> 70%) up to Zn contents of 99.5 mol% despite the segregation of ZnO. Operando spectroscopy, in combination with computational analysis, identifies the Zn-V-Hf motif as the active site for methanol formation that proceeds via the formate-methoxy pathway. Such active sites are not only present in solid solution-type ZnHfO catalysts (≤ 35 mol% Zn), but also in the form of isolated HfO clusters on segregated ZnO surfaces (for high Zn contents of > 35 mol%), explaining the high selectivity (and activity) over a wide range of Zn contents.
Fu T, Wei G, Wei Y
… +5 more, Tang B, Li L, Lützenkirchen-Hecht D, Yuan K, Chen Y
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42376801
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Dual-atom catalysts (DACs) provide a promising approach to overcome the linear scaling relationship that limits the activity of single-atom catalysts for oxygen reduction reactions (ORR). However, the lack of a direct el...Dual-atom catalysts (DACs) provide a promising approach to overcome the linear scaling relationship that limits the activity of single-atom catalysts for oxygen reduction reactions (ORR). However, the lack of a direct electronic bridge between the two sites, along with the inherently localized character of transition-metal 3d orbitals, often hinders coherent electronic regulation and efficient orbital overlap with reaction intermediates. Herein, inspired by the natural iron-sulfur clusters, we design an S-bridged Fe-Fe DAC (FeN-S/SNC). The sulfur bridge acts as an intrinsic charge-transfer channel, enabling strong electronic coupling between the Fe centers. Combined experimental and theoretical analyses demonstrate that this configuration promotes dynamic charge redistribution and enhances Fe 3d-S 2p orbital hybridization, which cooperatively optimizes oxygen intermediate adsorption and enhances the ORR kinetics. Consequently, FeN-S/SNC exhibits outstanding alkaline ORR performance with a half-wave potential of 0.93 V, a kinetic current of 35.40 A g, and a high turnover frequency of 2.49 e site s. When integrated into an ampere-hour-scale zinc-air battery, it delivers a discharge capacity of 4.76 Ah and a peak power of 2.67 W. This work demonstrates a bio-inspired bridging strategy to create electronically coherent dual-atom sites, offering fresh perspectives on the rational design of high-performance DACs for energy conversion devices.
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42376792
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Living systems organize electron flow through continuous, spatially and energetically structured redox networks, whereas most synthetic light-driven bioelectronic platforms rely on abiotic materials to generate and injec...Living systems organize electron flow through continuous, spatially and energetically structured redox networks, whereas most synthetic light-driven bioelectronic platforms rely on abiotic materials to generate and inject electrons into cells, limiting selective coupling between living partners. Here, we report programmable living electronic interfaces that enable direct, light-driven interspecies electron transfer (IET) between two living microorganisms. A conformal poly(3,4-ethylenedioxythiophene) network integrated into the envelope of Synechococcus elongatus intercepts and relays photosynthetic electron flux, while supramolecular cucurbit[7]uril host-guest interactions program defined cell-cell assembly with engineered Escherichia coli. Redox-active mediators embedded within the interface establish energetically matched electron-transfer pathways across species boundaries. Redox-potential matching identifies neutral red as an optimal mediator, enabling selective delivery of photosynthetic electrons into E. coli with an IET efficiency of 83.7%, thereby enhancing light-driven biocatalysis. This work establishes an integrated bio-bio electronic architecture that embeds electronic conduction within living redox networks, defining a paradigm for constructing light-powered microbial consortia distinct from conventional abiotic-bio hybrid systems.