Dong H, Zhu X, Chen SF
… +12 more, Liu H, Li C, Xu SW, Wei GX, Xia Y, Tang Y, Feng YH, Liu M, Chen K, Xiao B, Cheng Y, Wang PF
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42329130
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The practical application of high-energy-density P2-type cathodes is hindered by severe voltage decay upon high-potential cycling. This voltage decay primarily originates from irreversible interlayer cation migration and...The practical application of high-energy-density P2-type cathodes is hindered by severe voltage decay upon high-potential cycling. This voltage decay primarily originates from irreversible interlayer cation migration and detrimental structural degradation, which can be notably suppressed by regulating the arrangement of superstructure units. Herein, we incorporate LiTiMn superstructure units in P2-NaKLiNiMnTiO (NaKLNMT) to construct the long-range in-plane ordered arrangement within transition metal slabs, creating a stable oxygen coordination environment and high energy barriers along the migration path. Furthermore, the circumscribed P-type to O-type stacking evolution and restricted Li/TM migration restrain the formation of vacancy clusters, prohibiting consequential overoxidation of lattice oxygen and inhomogeneous lattice strain accumulation under high-voltage. Therefore, the target NaKLNMT compound exhibits a negligible voltage decay of 0.15 mV/cycle and 96.3% capacity retention over 100 cycles at 1 C. Our findings demonstrate that regulating cation migration through local superstructure control helps steer strategies to address the issues of voltage decay in sodium-layered oxide cathodes.
Chen D, Wang F, Lyu W
… +3 more, Chen L, Shen K, Li Y
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42323828
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Direct electroreduction of industrially diluted CO into CH represents a promising route for sustainable energy conversion, yet the selectivity and current density of this process are fundamentally constrained by the insu...Direct electroreduction of industrially diluted CO into CH represents a promising route for sustainable energy conversion, yet the selectivity and current density of this process are fundamentally constrained by the insufficient reactant concentration and generation of *CO intermediates. Herein, we addressed this issue by designing an ordered hollow sphere array nanoreactor with Cu nanoparticle and Ni single atom as the tandem catalytic sites (Cu-NP/Ni-NC OHSpA) using a unique reverse templating protocol. Mechanistic studies demonstrate that *CO can be generated on Ni site and undergoes spillover to the neighboring Cu particle. Significantly, the ordered hollow sphere array serves as effective CO reservoir to enhance the *CO coverage and thereby promote the C-C coupling to form CH. As a consequence, Cu-NP/Ni-NC OHSpA exhibits excellent electrocatalytic performance toward the conversion of diluted CO (i.e., 15% CO/Ar), affording a CH Faradaic efficiency (FE) of 57.5% with a partial current density (J) of 110 mA cm.
Wang FY, Prescimone A, Häussinger D
… +1 more, Tiefenbacher K
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42323820
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Macrodiolides are widespread motifs in functional molecules, yet their synthesis remains challenging. Existing methods typically still rely on high-dilution conditions to suppress undesired oligomerization, limiting effi...Macrodiolides are widespread motifs in functional molecules, yet their synthesis remains challenging. Existing methods typically still rely on high-dilution conditions to suppress undesired oligomerization, limiting efficiency and scalability. Therefore, developing macrocyclization strategies under non-dilute conditions remains a long-standing goal. Herein, we report a confinement approach to address this challenge by utilizing the spatial restriction and conformational preorganization provided by the hexameric resorcin[4]arene capsule. Such supramolecular confinement enables the cyclization of readily accessible diols and diacyl chlorides to afford 18-32-membered macrodiolides under non-dilute conditions and without the need for slow-addition procedures. Notably, the method also enables the one-pot formation of 26-32-membered macrotetrolides, a transformation that is difficult to achieve using conventional strategies, including high-dilution conditions. Compared with established ring-closing metathesis, this strategy offers higher efficiency, shorter synthetic routes, and access to more strained macrodiolides. Overall, these findings highlight the power of confinement catalysis for challenging macrocyclization reactions.
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42323818
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Activation of white phosphorus (P) to smaller P units by rare-earth compounds remains a synthetic challenge. Here, we show that the rare-earth dinitrogen complexes [{(Cp)M}(μ-1,2-N)] (M = Y, Gd; Cp = 1,2,4-tri(tert-butyl...Activation of white phosphorus (P) to smaller P units by rare-earth compounds remains a synthetic challenge. Here, we show that the rare-earth dinitrogen complexes [{(Cp)M}(μ-1,2-N)] (M = Y, Gd; Cp = 1,2,4-tri(tert-butyl)cyclopentadienyl), reductively cleave P to give a homologous series of phosphorus anions of decreasing nuclearity, that is, [{(Cp)M}(μ-P)] (1), [{(Cp)M}(μ-η:η-P)] (2), and [{(Cp)M}(μ-P)] (3). Structural, spectroscopic, and computational studies show that 1 contains a bicyclobutane-like [P] ligand, whereas 2 features a side-on coordinated [P═P] ligand, and 3 comprises a monatomic P ligand formulated as a phosphorus-centered radical with S = 1/2. The EPR spectrum of 3 confirms hyperfine coupling to P and Y, while magnetic measurements on 3 reveal strong antiferromagnetic exchange between the Gd ions and the radical ligand. Density functional theory supports a three-center π-type M-P-M interaction in 3, with the unpaired spin localized primarily on phosphorus and only weak delocalization onto the metal centers. These findings represent progressive fragmentation of P to diatomic and monatomic phosphorus anions by rare-earth reagents, thereby extending the chemistry of multiply bonded phosphorus and persistent phosphorus radicals into the rare-earth series.
Xie Z, Li B, Wu C
… +4 more, Li Z, Gao Z, Pan W, Liu B
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42323812
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Near-infrared (NIR) organic afterglow probes are attractive for deep-tissue, high-contrast bioimaging, yet simultaneously achieving white-light excitation, long-lived NIR phosphorescence, and uniform nanoparticle fabrica...Near-infrared (NIR) organic afterglow probes are attractive for deep-tissue, high-contrast bioimaging, yet simultaneously achieving white-light excitation, long-lived NIR phosphorescence, and uniform nanoparticle fabrication remains challenging. Herein, we develop a bottom-up route to lattice-matched host-guest nanocrystals by incorporating a rigid phenylcarbazole host (BMC) with scaffold-matched, extended-conjugation guests (PyC or BPC). The resulting doped crystals show guest-dominated deep-red/NIR afterglow, with the longest-wavelength vibronic band reaching 762 nm and can be activated by visible light up to 475 nm, delivering an ultralong lifetime of 126.1 ms and a phosphorescence quantum yield of up to 2.7%. Importantly, the intrinsic homogeneity of the lattice-matched incorporation enables direct formation of monodisperse phosphorescent nanoparticles via simple bottom-up nanoprecipitation, avoiding the size heterogeneity and material loss typically associated with top-down crystal fragmentation. These nanoparticles exhibit negligible cytotoxicity and deliver bright, persistent deep-red/NIR emission under white-light excitation for high-contrast in vivo imaging.
Zeng M, Lou Y, Sheng T
… +6 more, Xi C, Yan Z, Yang X, Bai Y, Cheng HM, Xing G
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42323810
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Tin-lead (Sn-Pb) mixed perovskites have propelled all-perovskite tandem solar cells (APTSCs) beyond 30% efficiency, yet buried-interface instability impedes commercialization. The ubiquitous PEDOT:PSS layer readily facil...Tin-lead (Sn-Pb) mixed perovskites have propelled all-perovskite tandem solar cells (APTSCs) beyond 30% efficiency, yet buried-interface instability impedes commercialization. The ubiquitous PEDOT:PSS layer readily facilitates the oxidation of I, and the subsequent diffusion of corrosive I severely compromises device performance-a fundamental chemical degradation pathway that leaves unresolved. Here, we introduce 6-amino-2-thiouracil (ATU) as a multifunctional additive that chemically targets this degradation pathway. Embedded within the PEDOT:PSS layer, the interaction between ATU and PSS contributes to alleviating the oxidation of I while its C═S moiety actively reduces corrosive I back to I, establishing a dynamic iodine-recycling mechanism that addresses the root chemical cause of instability. Concurrent defect passivation and crystallization modulation further enhance film quality. Benefiting from these synergistic effects, the optimized APTSCs achieve a champion efficiency of 29.29% (certified 28.79%) and exhibit significantly improved stability, maintaining over 85% of their initial efficiency after 500 h of maximum power point tracking. By targeting buried-interface corrosive I, this work provides a rational framework beyond conventional passivation for durable perovskite photovoltaics.
Xie Z, Liu H, Yang Y
… +12 more, Sun X, Wang J, Liu T, Wang B, Qiu W, Sun Y, Bai Y, Zhang Y, Ma D, Xiang R, Li S, Xi Z
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42323807
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Derivatives of deoxyribose cyclic dinucleotides (dCDNs) displayed notable advantageous properties in the activation of STING pathway. The chirality of the phosphotriester of dCDN prodrugs may influence the stability, cel...Derivatives of deoxyribose cyclic dinucleotides (dCDNs) displayed notable advantageous properties in the activation of STING pathway. The chirality of the phosphotriester of dCDN prodrugs may influence the stability, cellular permeability, bioactivity and duration, which remains inadequately explored through systematic evaluations in cellular and animal models. Herein, we isolated and characterized all three diastereoisomers of alkyne-conjugated esterase-sensitive dCDN prodrugs, and meticulously examined their difference in stability, cellular uptake and bioactivity. Within THP1 cells, the (Rp,Rp) diastereoisomer demonstrated the highest level of activation of STING pathway (EC = 1.7 nM), and induced more robust and prolonged activation pulse than the (Rp,Sp) and (Sp,Sp) diastereoisomers. In murine models, prodrugs elicited significantly stronger stimulation in the development of an antitumor immune response compared to the parent CDN 3',3'-c-di-dAMP, as well as the clinically relevant STING agonist ADU-S100. The (Rp,Rp) diastereoisomer exhibited the most pronounced antitumor activity in the context of intravenous administration, significantly suppressing tumor proliferation, extending the survival with a complete response (CR) rate of 90% in a mouse CT26 tumor model, and establishing long-lasting tumor-specific immunological memory. These findings underscore the importance of considering the chirality of phosphotriesters in the development of more effective, safer, and sustainable STING agonist in tumor immunotherapy.
Ren Y, Qu H, Nilles J
… +4 more, Miao Z, Li Y, Chen LH, Su BL
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42323806
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Lithium-nitrogen (Li-N) batteries offer a unique electrochemical paradigm that combines intrinsically safe energy storage with sustainable N conversion to value-added chemicals. About ten years after the first ground-bre...Lithium-nitrogen (Li-N) batteries offer a unique electrochemical paradigm that combines intrinsically safe energy storage with sustainable N conversion to value-added chemicals. About ten years after the first ground-breaking report, the practical development of Li-N batteries is still restricted by poor reversibility and limited cycling stability. Here, we first introduce this highly innovative and promising Li-N battery technology and then specify the key challenges ahead for the poor reversibility of Li-N batteries from reaction mechanisms, characterization technologies, and the battery configurations. We further highlight a flow field-assisted "flow-type" cell configuration that presents exciting future opportunities to realize reversible Li-N batteries. Besides, we discuss that the diversity in terms of electrolytes, electrode materials, and separators is key to establishing long-term Li-N batteries. The possible mechanistic pathways of N reduction and lithiation over heterogeneous electrocatalysts are also discussed. We recommend a rigorous experimental protocol for evaluating Li-N batteries to ensure reproducibility and reliable performance comparison across studies. Overall, this perspective aims to inspire future generations of researchers to advance both fundamental understanding and practical breakthroughs, thereby engineering a paradigm shift in Li-N chemistry research.
Wang M, Fang W, Cai L
… +7 more, Zhu D, Shi Y, Guo W, Zhang X, You B, Song F, Xia BY
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42323804
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Direct electrochemical conversion of industrial flue gas offers a promising route to carbon neutrality, but it remains limited by trace sulfur dioxide (SO, 10-400 ppm) impurities. These impurities cause rapid catalyst de...Direct electrochemical conversion of industrial flue gas offers a promising route to carbon neutrality, but it remains limited by trace sulfur dioxide (SO, 10-400 ppm) impurities. These impurities cause rapid catalyst deactivation, particularly under the high reaction rates required for industrial application. Here, we introduce a hydrophobic molecular gate strategy to decouple impurity transport from catalyst deactivation. By regulating the interfacial water solvation structure and proton transfer pathways, this design creates a water-deficient regime to lock the kinetic switch. As a result, SO is isolated from the hydrogen-mediated reduction, while the transient water required for efficient CO conversion is preserved. When paired with a lattice-strained copper catalyst, this architecture allows a scaled-up 100 cm membrane electrode assembly (MEA) to operate at a total current of 20 A for over 120 h, maintaining an ethylene (CH) Faradaic efficiency (FE) >56% in simulated flue gas.
Däther M, Peev E, Fröhlich A
… +15 more, Vick B, Fatourechi S, Gasparoni G, Heiss M, Pleintinger CC, Bisong EA, Hurmiz H, Guglielminotti D, Gärtner YV, Aumer T, Spiekermann K, Walter J, Jeremias I, Traube FR, Carell T
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42323802
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Ten-eleven translocation (TET) enzymes are critical epigenetic regulators, which oxidize the methylated cytosine nucleobase 5-methyl-dC (mdC) in the genome to 5-hydroxymethyl-dC (hmdC) in an α-ketoglutarate-dependent man...Ten-eleven translocation (TET) enzymes are critical epigenetic regulators, which oxidize the methylated cytosine nucleobase 5-methyl-dC (mdC) in the genome to 5-hydroxymethyl-dC (hmdC) in an α-ketoglutarate-dependent manner. Because the presence of mdC in the promoter region of a given gene silences its expression, this oxidation goes in hand with the reactivation of such silenced genes. In different highly aggressive cancers such as acute myeloid leukemia (AML) and glioblastoma, loss of TET enzyme function, and therefore reduced hmdC levels pave the way for tumor development. Impairment of TET activity can occur through metabolic inhibition, through loss-of-function mutations in TET genes themselves, and finally through suppression of TET-expression via epigenetic silencing. Reactivation of TET enzyme expression represents a major aim of epigenetic cancer therapy. Here we show that the carbocyclic antimetabolite 5-aza-2'deoxycytidine (cAzadC), which is supposed to suppress the methylation of DNA during replication, leads to a substantial increase of TET2 expression and strongly increasing hmdC levels. We show that the treatment with cAzadC goes in hand with the broad reactivation of the cellular antitumor responses. With patient-derived xenograft AML-mouse models, we show that this translates into a strongly improved anticancer effect in vivo.
Nadeem RY, Fang P, Shi Y
… +6 more, Wang J, Yuan B, Zhang X, Kong X, Wang C, Du P
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42323801
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Herein, we present a new class of hybrid conjugated polymer that integrates [8]cycloparaphenylene ([8]CPP) directly into poly(para-phenylene vinylene) (PPV) frameworks, creating a π-extended poly(cyclo(para-phenylene vin...Herein, we present a new class of hybrid conjugated polymer that integrates [8]cycloparaphenylene ([8]CPP) directly into poly(para-phenylene vinylene) (PPV) frameworks, creating a π-extended poly(cyclo(para-phenylene vinylene)) ([8]CPPV). Comprehensive characterization confirmed its well-defined alternating structure. Photophysical analyses revealed curvature-driven electronic coupling between the radial CPP and linear PPV π-systems, resulting in broadened absorption, red-shifted emission, and high fluorescence quantum yield. Furthermore, [8]CPPV demonstrates excellent performance as a lithium-ion battery anode, combining high initial capacity with stable cycling enabled by mixed pseudocapacitive and diffusion-controlled Li storage mechanisms. These results establish [8]CPPV as a versatile all-carbon polymeric framework that bridges molecular nanohoops and extended π-networks, offering a tunable platform for optoelectronic and energy storage applications.
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42323799
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The increasing prominence of stereogenic-at-sulfur motifs in drug discovery and catalysis has created a growing demand for versatile synthetic methods. We describe here an Fe(PDP)-catalyzed enantioselective NH-amination...The increasing prominence of stereogenic-at-sulfur motifs in drug discovery and catalysis has created a growing demand for versatile synthetic methods. We describe here an Fe(PDP)-catalyzed enantioselective NH-amination of sulfenamides to access chiral sulfinamidines. This method accommodates a broad range of sulfenamides, enabling direct access to diverse nitrogenated stereogenic-at-sulfur architectures. The synthetic utility is demonstrated by the efficient preparation of pharmaceutically relevant compounds, such as an aza-analog of drug candidate LY181984 and a PP2A modulator. Moreover, this reaction represents the first example of asymmetric NH transfer using the widely employed bioinspired Fe(PDP)-type catalysts.
Gao P, Zhang J, Geng Y
… +3 more, Jiang C, Cui Y, Gong W
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42323798
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Rational design and serendipitous discovery constitute the two wheels of molecular science. Despite the fruitful achievements of constructing metal-organic frameworks from highly symmetric linkers under the guidance of r...Rational design and serendipitous discovery constitute the two wheels of molecular science. Despite the fruitful achievements of constructing metal-organic frameworks from highly symmetric linkers under the guidance of reticular chemistry principles, the formulation of synthetic principles with unsymmetric organic linkers, while fundamentally important for targeting unexpected structures and functions, has been underdeveloped. Herein, we achieved a Zr(IV)-based MOF (SJTU-24) with a computationally modelled trinodal (3,4,8)-connected eft topology where two types of Zr secondary building units (SBUs) co-exist, including an unprecedented 4-connected concave coordination figure, through a complete linker desymmetrization approach. This topology, to our knowledge, has not been experimentally achieved in Zr-based MOFs, highlighting the pivotal role of linker symmetry manipulation in the discovery of materials with non-default topology. SJTU-24 exhibits exceptional ammonia capture performance among Zr-based MOFs, reaching 14.1 and 4.8 mmol/g adsorption capacity at 1 and 0.1 bar, respectively. Semi-in situ Infrared (IR) and x-ray photoelectron spectroscopic (XPS) studies decipher that both the Brønsted acidic hydroxyl sites in the Zr SBUs and the monodentately-coordinated carboxylate moieties in the linkers participate in the interactions with NH. This work, thus provides a valuable insight into leveraging complete linker desymmetrization engineering to unlock non-default and sophisticated structures with improved properties.
Fernández-Carrión AJ, Xu H, Ming X
… +9 more, Rakhmatullin A, Li C, Wang J, Porcher F, Ma X, Zhang X, Pitcher MJ, Allix M, Kuang X
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42322209
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Characterizing structural disorder in solids is of significant challenge, which requires new strategy on probing and describing local structures over different scales and uncovering coherent ordering hidden in the struct...Characterizing structural disorder in solids is of significant challenge, which requires new strategy on probing and describing local structures over different scales and uncovering coherent ordering hidden in the structural disorder. Herein, we demonstrate a multimodal solution for structural disorder in Na Mg Si O sodium-ion electrolytes with a stuffed cristobalite tetrahedral network. Neutron pair distribution function analysis combined with reverse Monte Carlo simulations was employed to probe the structural disorder in nanometer-scale supercells, uncovering the hidden correlated Mg/Si disorder or local Mg/Si order forming neighboring pure Mg (or Mg-rich) and Si columns. This correlated disorder was further validated by solid state Si nuclear magnetic resonance (NMR) spectroscopy and NMR-guided structure screenings. The sodium cations in the tunnels were proposed to be interstitial-like mobile charge carriers for ionic conduction in Na Mg Si O referring to the parent cristobalite structure. Both sodium contents within the tunnels and structural disorder level play competing roles in the sodium migration, while local Mg/Si order may minimize distortion of tetrahedral network and therefore maximize the tunnel bottlenecks promoting sodium migration. This work provides practicable multimodal solution strategy to solve the commonly complex structural disorders and unveil inherently local order with wide applicability in functional materials, enhancing understanding of structure-property relationship.
Zhou L, Li C, Yang X
… +10 more, Zhang J, Qin S, Sun W, Xia X, Meng L, Zhang M, Yan H, Song B, Li X, Li Y
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42322196
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Dimeric acceptors have recently emerged as promising giant molecule acceptors (GMAs) for organic solar cells (OSCs), but most systems link two identical monomeric units. Hybrid GMAs combining different acceptor units rem...Dimeric acceptors have recently emerged as promising giant molecule acceptors (GMAs) for organic solar cells (OSCs), but most systems link two identical monomeric units. Hybrid GMAs combining different acceptor units remain unexplored. Herein, we develop a core-to-wing type hybrid strategy coupling BT- and BZ-core acceptor units through flexible ester-linked alkyl chains, affording three GMAs (BTZ-2-2, BTZ-2-6, and BTZ-2-10). This design enables complementary absorption by combining the spectral features of BT- and BZ-based monomers while preserving favorable crystallization behavior. Among them, BTZ-2-6 exhibits the broadest, most red-shifted absorption, enhanced π-π stacking, and the highest electron mobility due to the optimal length of its ester-linked alkyl chain. The PM6:BTZ-2-6 binary device delivers 18.53% efficiency and retains nearly 90% of its initial efficiency after 720 h of illumination. Furthermore, the efficiency can be increased to 19.41% by replacing PM6 with D18 as the donor polymer, and further boosted to 20.25% by incorporating BTZ-2-6 as a third component into PM6:L8-BO binary devices. These results demonstrate that core-to-wing hybrid GMAs with ester-linked alkyl chains of different lengths provide an effective strategy for constructing high-performance GMAs, offering new opportunities for efficient and stable OSCs.
Ma J, Chang P, Yang S
… +3 more, Li Z, Liu Y, Wang J
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42322194
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The recovery of gold from electronic waste is a sustainable and eco-friendly resource recycling strategy. However, simultaneously achieving high adsorption capacity, rapid kinetics, and exceptional selectivity remains a...The recovery of gold from electronic waste is a sustainable and eco-friendly resource recycling strategy. However, simultaneously achieving high adsorption capacity, rapid kinetics, and exceptional selectivity remains a significant challenge. Herein, a novel approach was presented for efficient gold recovery by photothermal effect in one-dimensional covalent organic frameworks (1D-COFs), and TN-COF and TC-COF were designed and synthesized for such studies. Under visible light irradiation, they exhibited excellent AuCl adsorption capacity (3489 and 3340 mg g), ultrafast adsorption kinetics (over 99% gold removal within 20 s), good recyclability (> 25 cycles) and high selectivity (K > 1.0 × 10 mL g, S > 9.0 × 10), which enable about 99% gold recovery from waste central processing unit (CPU) leachates with only 17 ppm Au(III), ranking among the highest values reported for COF-based adsorbents to date. Mechanistic results revealed that Au(III) was adsorbed by electrostatic and coordination interactions with multiple N and O sites, while both protonated ─NH group and photogenerated electrons efficiently reduced the adsorbed Au(III) to Au(0). By leveraging the photothermal properties of the COFs, a synergistic photoreduction-thermal promotion strategy was established to surpass traditional exothermic adsorption, enabling rapid and high-capacity gold recovery via an endothermic-reduction-driven equilibrium shift under visible light.
Tao H, Chen Y, He S
… +6 more, Chen B, Shang Z, Ma Z, Liu X, Chai L, Lin Z
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42322169
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Publisher ↗
Electrochemical oxidative dehydrogenation (ODH) of ethane in solid oxide electrolysis cells (SOECs) offers an energy-efficient route to ethylene but faces a trade-off between conversion and selectivity due to over-oxidat...Electrochemical oxidative dehydrogenation (ODH) of ethane in solid oxide electrolysis cells (SOECs) offers an energy-efficient route to ethylene but faces a trade-off between conversion and selectivity due to over-oxidation. Conventional voltage-current regulation can suppress deep oxidation but inevitably compromises ethane conversion. Here, we engineer surface electronic structures by depositing a VO layer on SrFeTiO (STF), introducing intrinsic O 2p (-1.33 eV) and V 3d (-0.18 eV) states closer to the Fermi level than in STF (-1.49/-4.52 eV). Density functional theory and operando infrared spectroscopy reveal three synergistic effects: enhanced ethane adsorption (ΔE -0.33 vs. -0.11 eV), reduced first dehydrogenation barrier (ΔG 1.13 vs. 1.15 eV), and promoted ethylene desorption ((ΔG-ΔG) -4.98 vs. -1.92 eV). The optimized anode delivers 65% yield and 90% selectivity at 750°C, exceeding unmodified STF by 10%. This work highlights band-center engineering as a promising design concept for regulating hydrocarbon electrode reactions.
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42322164
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Publisher ↗
The insertion of five-membered heteroarenes into the C─C bonds of benzocyclobutenones (BCBs) has been achieved. This process proceeds under mild conditions and does not require the use of a transition metal catalyst. A v...The insertion of five-membered heteroarenes into the C─C bonds of benzocyclobutenones (BCBs) has been achieved. This process proceeds under mild conditions and does not require the use of a transition metal catalyst. A variety of fused polycyclic compounds based on indoles, 7-azaindoles, benzothiophenes, benzofurans, and thiophenes relevant to bioactive scaffolds are efficiently accessed through this approach. The reaction is scalable, and the products are suitable for various late-stage derivatizations. Preliminary mechanistic studies reveal a catalytic role of base in facilitating C─C bond cleavage to generate a reactive intermediate which likely engages in subsequent dearomative cycloaddition with heteroarenes.
Lal A, Mridula K, Madhusudhanan MC
… +2 more, Siddharthan A, Sureshan KM
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42322162
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Accessing structurally well-defined polymer polymorphs remains extremely challenging because obtaining polymer single crystals suitable for atomic-level structural characterization is rare. Here we report an unusual sequ...Accessing structurally well-defined polymer polymorphs remains extremely challenging because obtaining polymer single crystals suitable for atomic-level structural characterization is rare. Here we report an unusual sequence of single-crystal transformations in which a peptide monomer designed for topochemical azide-alkyne cycloaddition (TAAC) undergoes spontaneous single-crystal-to-single-crystal (SCSC) polymerization to form a 1,4-triazolyl-linked polymer, despite a crystal packing seemingly predisposed for the formation of a 1,5-linked product. Structural and computational analyses reveal that large-amplitude rotations of the azide and alkyne groups enable the unexpected regioselectivity. Prolonged heating subsequently triggers a rare SCSC polymorphic transition of the polymer crystal, generating a second conformational polymorph with distinct chain packing and mechanical properties. These results demonstrate that sequential single-crystal transformations can provide controlled access to polymer polymorphs from a single monomer crystal.
Li S, Liu J, Zhao M
… +5 more, Wang Q, Zhang J, Wang X, Yu ZZ, Li X
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42322161
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Publisher ↗
Intrinsic luminescence in polymer hydrogels is highly desirable for soft optoelectronic and information-security applications, yet remains difficult to achieve under hydrated conditions, where clusterization-triggered em...Intrinsic luminescence in polymer hydrogels is highly desirable for soft optoelectronic and information-security applications, yet remains difficult to achieve under hydrated conditions, where clusterization-triggered emission (CTE) is easily quenched by water due to disrupted intermolecular interactions. Here, we establish a facile and general strategy to overcome this limitation via directional freezing-assisted cryo-polymerization. The anisotropic growth of ice crystals imposes spatial confinement during network formation, driving dense chain packing and stabilizing amide-based emissive clusters. Such structural confinement suppresses nonradiative decay and enables a robust CTE effect even at ultrahigh water content (∼90 wt%), effectively overcoming the long-standing challenge of hydration-induced quenching. The resulting polyacrylamide hydrogel exhibits stable blue emission, structural stability, excellent resistance to water-induced quenching, and mechanical softness with elasticity and shape programmability, enabling rewritable and multilevel information encryption. More broadly, this work demonstrates that stable intrinsic luminescence in water-rich soft materials can be achieved through structural confinement rather than molecular modification, providing a general design principle for CTE systems and opening new opportunities for integrating optical functionality with structural programmability in soft materials.