The change in the central atom in the series of vanadium-doped Keggin-type polyoxotungstate clusters results in the near-perfect thermal compensation between redox potential and proton affinity. Despite identical driving forces, this series of polyoxotungstate clusters exhibits distinguished different proton–coupled electron transfer mechanisms toward the dehydrogenating of organic substrates.

The design of H-atom transfer catalysts requires the control of redox potential and proton affinity to direct the mechanism, rate, and selectivity of proton–coupled electron transfer (PCET). In the present study, we demonstrate that a series of reduced and protonated vanadium-substituted Keggin-type polyoxotungstates ([XVW11O39(OH)]n–, X = Si, n = 5; X = P, n = 4; X = S, n = 3), exhibit invariant bond dissociation free energies of surface O─H bonds (BDFE(O─H)s). Despite uniform driving forces for H-atom uptake, kinetic analysis with a variety of H-atom donors (5,10-dihydrophenazine, hydrazobenzene, and hydroquinones) reveals differences in rates of substrate oxidation, which are ascribed to disparate PCET mechanisms. Together, these findings show that substitution at the central heteroatom tunes the electron- and proton-transfer driving forces (ΔG PT and ΔG ET) thereby dictating the operative PCET mechanism.

Unlike liquid water, the structural and molecular properties of water molecules embedded in hydrated salts are subject to strong influences and vary little. This makes them potential candidates for the water splitting reaction. Here, we present the first example of the electrochemical decomposition of crystallised water.

In contrast to the liquid phase of water, the structural molecular realities of H2O molecules embedded in crystallised salts vary little and can be precisely determined. However, this water, which is neither in the liquid nor in the gas phase, has not yet been used in water electrolysis. Here, we demonstrate that water electrolysis can be achieved without the addition of (liquid) water through experiments with a wide range of hydrated salts and organic solvent suspensions. We obtain an excellent correlation between the position of the FTIR O─H stretch vibration of the hydrated salts and the onset of the OER potential from CV measurements. Together with first-principles density functional theory calculations, we demonstrate that intramolecular bonds in crystallised water can be effectively controlled through choice of the inorganic salt. Targeted manipulation of the bonds in the H2O molecule is a promising new approach to more efficient hydrogen production.

The present work showcases a photoenzymatic platform using bromoacetonitrile as a practical cyanide source for asymmetric γ-hydrocyanation of alkenes. The system enables direct activation of inert aliphatic C─Br bonds via engineered ene-reductases (PETNR H182M) under visible light. Remarkably, the enzyme achieves excellent enantiocontrol through stereoselective hydrogen atom transfer within its active site

Enzymatic strategies for direct cyano group incorporation remain underdeveloped, creating synthetic bottlenecks for accessing chiral nitrile derivatives in pharmaceuticals and functional materials. Herein, we have developed a photoenzymatic γ-hydrocyanation strategy that addresses this gap. The system demonstrates remarkable efficiency in activating the challenging aliphatic C─Br bond of bromoacetonitrile through engineered ene-reductase catalysis. Upon visible light excitation, the reduced flavin cofactor generates cyanomethyl radicals that are spatially confined and precisely oriented within the enzyme's active site for efficient coupling with α-methylstyrenes. This synergistic photoenzymatic system also demonstrates distinct stereochemical control, with the engineered active site simultaneously governing radical generation and subsequent enantioselective hydrogen atom transfer to afford a large range of γ-stereogenic nitriles in up to 93% yield, 94% ee – a transformation that poses considerable challenges for traditional transition metal catalysis. Beyond providing a robust platform for asymmetric cyanoalkylation, this work significantly advances photoenzymatic catalysis by establishing unactivated alkyl bromides as viable radical precursors for selective bond formations.

Comprehensive analyses of two enzyme classes from the amidohydrolase superfamily (AHS) revealed that catalysis proceeds either via 1,4 or 1,6 nucleophilic conjugate addition and that this property defines substrate specificity. Moreover, although all substrates and products are entirely achiral, this mechanistic difference results in an inverted enantioselectivity for fleeting chiral intermediates in the two analyzed AHS classes.

The sequencing of numerous genomes has led to the identification of open reading frames for millions of enzymes, many of which use unknown substrates. Hence, the identification of both primary and promiscuous activities remains a major challenge for enzyme research. Here, we identified the mechanistic basis of substrate specificity for members of the amidohydrolase superfamily (AHS). Comprehensive analyses of two AHS classes revealed that catalysis proceeds either via 1,4 or 1,6 nucleophilic conjugate addition mediated by a glutamine that is located at two different positions within the active site thereby shaping substrate scope in these enzymes. These different enzymatic properties result in an inverted enantioselectivity for fleeting chiral intermediates, which are transient chiral species on the reaction pathway from an achiral substrate to an achiral product. Moreover, we demonstrated that catalysis focuses on conserved core structures rather than on all moieties of a given substrate, which increases the degree of promiscuity and evolvability in these enzymes. Using site-directed mutagenesis, we showed that an enzyme specialized in a specific nucleophilic conjugate addition can both readily adapt to secondary substrates and accommodate novel substrates by few amino acid exchanges. Hence, our study reveals mechanistic principles that underly substrate specificity, promiscuity, and enantioselectivity.

Small-angle neutron scattering was used to probe porosity changes in the high-q range (0.06–0.4 Å−1) of a highly crystalline Tb-mesoMOF. The appearance of a broad scattering feature at low-q (∼0.005 Å−1) in Cyt. c@Tb-mesoMOF indicates enzyme clustering within the framework across long-range length scales.

The molecular-level investigation of enzyme behavior in confined, cell-free environments is essential to understanding intrinsic properties and optimizing systems for desired functions. Metal–organic frameworks (MOFs) provide unique structural features that enable the immobilization of bulky biomolecules and allow direct probing of enzymatic behavior under confinement. Here, small-angle neutron scattering (SANS) was employed to probe porosity changes in a highly crystalline Tb-mesoMOF and to reveal the spatial arrangement of encapsulated enzymes across long-range length scales. Structural characteristics such as framework void space were resolved by SANS, while contrast-matching experiments using D2O/H2O mixtures suppressed background scattering from the MOF and isolated the enzyme contribution. Compared to unloaded Tb-mesoMOF, cytochrome c (Cyt. c)-loaded Tb-mesoMOF exhibited the emergence of a broad scattering feature at low q (∼0.005 Å−1), indicative of enzyme clustering within the framework, accompanied by enhanced loading rate and capacity. Additional structural analyses using complementary techniques further corroborated these findings.

Systematic screening identifies Ru nanoparticles on carbon black (RuNP/C) as an efficient electrocatalyst for acetone hydrogenation via a hydrogen atom transfer pathway, enabled by optimized acetone and hydrogen adsorption. RuNP/C achieves 95% isopropanol Faradaic efficiency at 250 mA cm−2 and 99% single-pass conversion in the membrane electrode assembly, and selectively hydrogenates diverse ketones to secondary alcohols.

Secondary alcohols are indispensable building blocks in the production of fine chemicals, pharmaceuticals, and polymers, yet their conventional synthesis routes are energy and resource intensive. Electrochemical ketone hydrogenation under ambient conditions offers an attractive approach to synthesize secondary alcohols, but this process is often hindered by base-catalyzed self-condensation, hydrogenolysis, and competitive hydrogen evolution reaction (HER). Herein, we demonstrate that Ru nanoparticles supported on commercial carbon black (RuNP/C) can enable efficient, selective, and stable electrochemical hydrogenation of a wide range of structurally diverse ketones to produce corresponding secondary alcohols under ambient conditions. Mechanistic investigations reveal that RuNP/C can simultaneously promote generation of reactive hydrogen species and adsorption of ketone molecules, facilitating rapid transfer of reactive hydrogen species to adsorbed ketone molecules, thereby enabling efficient secondary alcohols formation and suppressing HER. This work opens a green and sustainable pathway for ketone upgrading.

A highly modular, three-component coassembly system has been developed that achieves high-fidelity integration of chiral functions on a cavitand. The resorcin[4]arene-derived cavitand, embedded with a sequential hydrogen bonding donor–acceptor array of benzimidazoles, enables corral encapsulation of chiral carboxylic acids and alcohols, promoting the deracemization of the corrals with propeller chirality.

Rational assembly of multiple molecular building blocks enables functional integration. However, precise construction of complex systems comprising of three or more molecular modules is challenging due to the pathway complexity. Here, we report a highly modular, three-component coassembly system that achieves high-fidelity integration of chiral functions on a cavitand. The resorcin[4]arene-derived cavitand, embedded with a sequential hydrogen bonding donor–acceptor array of benzimidazoles, enables corral encapsulation of chiral carboxylic acids and alcohols, promoting the deracemization of the corrals with propeller chirality. This approach allows for the unprecedented construction of modular supramolecular-chiral cavitand. After installing chiral acid module on corral, the cavity is expanded that could further include a guest molecule as a third module. Chirality was successfully transferred from the cavitand to the luminescent module, resulting in efficient circularly polarized luminescence. This study leverages the propeller chirality of deep cavitands to construct a highly modular, functionally integrated molecular system, demonstrating great potential for building customizable and disassemblable molecular functional platforms.

We present a photoswitchable peptide conjugate which exhibits isomerism-dependent self-assembly: the planar trans-isomer assembles into well-ordered nanofibers while the non-planar cis-isomer yields disordered aggregates. Our study offers a direct visualization on the effects of structure formation inside living cells.

Understanding how self-assembled structure formation affects cells remains a central challenge in supramolecular chemistry. However, chemical tools that allow access to both ordered and disordered intracellular assemblies from a single molecular scaffold are rare due to design complexity. Here, we present a photoswitchable isotripeptide incorporating an arylazopyrazole (AAP) unit, which undergoes intracellular cleavage to yield a self-assembling monomer. Upon photoisomerization, the planar trans-isomer forms β-sheet-rich nanofibers with strong aromatic interactions, while the non-planar cis-isomer assembles into disordered, random-coil aggregates lacking aromatic contribution. The structural dynamics of the assemblies are demonstrated by repeated photoswitching between the two states in buffered conditions. Notably, A549 cancer cell viability correlates with the isomer-dependent assembly behavior and critical aggregation concentrations (CACs): the trans-isomer, with higher aggregation propensity, exhibits greater cytotoxicity. This photoswitchable peptide system thus provides a powerful platform with fast, reversible and robust switching kinetics, long isomer half-lives, and high photostability to probe the intracellular consequences of supramolecular order and disorder using a single molecular scaffold.

Controlling the regioselectivity of Alder-ene reactions with unsymmetrical alkynes remains a significant challenge. Here, we demonstrate that propargyl B(MIDA)-substituted alkynes serve as effective substrates for regiodivergent Alder-ene reactions. By selecting either [CpRu] or [Cp*Ru] catalysts, we can selectively access linear or branched 1,4-dienes via γ- or β-allylation, respectively. Mechanistic studies indicate that the B(MIDA) group exerts a unique stereo-electronic effect responsible for this regiocontrol.

1,4-Dienes are pivotal structural motifs in bioactive natural products and serve as valuable intermediates in synthetic chemistry. Among the various methods for their synthesis, the ruthenium-catalyzed Alder-ene reaction stands out due to its redox-neutral, atom- and step-efficient nature. However, controlling regioselectivity with unsymmetrical alkynes remains a persistent challenge. In this study, we demonstrate that propargyl B(MIDA)-substituted alkynes are effective substrates for regio-divergent Alder-ene reactions. By selecting between [CpRu] and [Cp*Ru] catalysts, we can selectively obtain either linear or branched 1,4-dienes via γ- or β-allylation. Mechanistic investigations reveal that σ(C─B)→σ(Ru─C)* hyperconjugation plays a critical role for γ-selectivity, while steric repulsion between the Cp* ligand and the bulky B(MIDA) group governs the β-selectivity. This approach provides a straightforward and efficient means to access two distinct allylic boron-functionalized 1,4-dienes, each featuring differentiated double bonds, which are highly amenable to further chemical elaboration.

Catalytic self-assembling peptides (cSAPs) form fibrils that catalyze the retro-aldol reaction of Methodol. Co-assembly with inactive peptides tunes catalytic efficiency by altering substrate accessibility and the distance to the nucleophilic lysine. This approach enables precise engineering of catalytic domains and activities in peptide-based catalytic nanostructures.

Short peptide sequences self-assemble into supramolecular structures through intermolecular interactions, creating a microenvironment in which chemical reactions can be catalyzed. In recent years, many peptide sequences have shown to demonstrate catalytic activity upon nanostructure formation, but the engineering of the catalytic microenvironment through co-assembly strategies have not been explored. We introduce a peptide sequence that gains retro-aldolase activity upon assembly to supramolecular peptide fibrils in aqueous buffer solution (pH 7.4). The catalytic activity is first optimized through synthetic sequence variation and the structure formation properties of the peptides are characterized. Co-assembly with inactive peptide sequences enables the up- or downregulation of the catalytic activity over a dynamic range, by modulating the likelihood for substrate interaction and thus the distance of the substrate to the nucleophilic lysine at the active site. It is observed that co-assemblies with positively charged sequences increase activity, whereas negatively charged peptide sequences decrease activity. We show that the emerging field of peptide-based catalysts can be further advanced by the engineering of the catalytic domain using heterogeneous supramolecular assembly.

This study develops a novel fluorescent NO2 sensor using a newl fabricated β-ketoenamine-linked COF membrane. It shows ultrafast response/recovery (1.5 s/2.0 s), high selectivity, a 0.1 ppm detection limit, and stability over 5000 tests. Its practical use is proven by real-time monitoring of vehicle exhaust and waste incineration emissions, enabled by its porous, electron-rich structure.

Developing compact and structurally simple sensors for reliable and rapid monitoring of nitrogen dioxide (NO2) remains a challenge. In this study, we synthesized a novel β-ketoenamine-linked 4 + 3 covalent organic framework (COF) membrane with unique topology structure using tetrakis(4-aminophenyl)ethene (ETTA) and 1,3,5-triformylphloroglucinol (TP) as monomers through liquid-liquid interfacial polymerization. The sensitive NO2 response of the ETTA-TP COF membrane enables the creation of the first and high-performance NO2 film-based fluorescent sensor, achieving fastest response/recovery time (1.5 s/2.0 s) and a high selectivity (over 16 potential interferents). This sensor realizes a low detection limit of 0.1 ppm and a broad detection range from 0.1 to 50 ppm, while maintaining stable performance over 5000 continuous tests. Furthermore, it demonstrates on-site, real-time monitoring of NO2 emissions from automotive exhaust and waste incineration. The sensing mechanism studies reveal that the carbonyl groups of β-ketoenamine structure can bind NO2 via electrostatic interactions and undergoes an energy-level-matching photoinduced electron transfer process under photoexcitation. The responses of other carbonyl-containing fluorescent molecules and COF materials to NO2 corroborate the generality of this mechanism. This study offers valuable insights into the development of oxidizing gas sensors characterized by fast response time, high sensitivity, and robust in situ online monitoring capabilities.

A multifunctional CYP450 enzyme from Antrodia camphorata, AcCYP1, not only catalyzes the C21 and C15 oxidation of lanosterol, but also mediates a C14–C15 methyl migration to produce a rare triterpene skeleton. This finding reveals a novel enzymatic approach to expand the diversity of triterpene skeleton and facilitates the de novo heterologous synthesis of high-value lanostane triterpenoids.

Lanostane triterpenoids, key therapeutic components of medicinal mushrooms, such as rare Antrodia camphorata, face heterologous biosynthesis barriers due to the lack of enzymes for essential C21/C15 oxidation and skeletal rearrangement, limiting access to these rare therapeutics. In this study, we deciphered these missing steps through the characterization of a single CYP450 enzyme, AcCYP1. Notably, AcCYP1 not only catalyzes the indispensable C21 and C15 oxidations, but also represents the first CYP450 enzyme identified to directly rearrange a triterpenoid backbone. This rearrangement generates the uncommon lanostane skeleton characterized by a Δ14(15) double bond and a C15 methyl group by disrupting canonical hydroxyl rebound and triggering cation-initiated rearrangement. Mechanistically, the catalytic performance of AcCYP1 is regulated by proximal active-pocket geometry and distal hydrophobicity. Mutating the key residue N520 markedly enhanced enzymatic activity, enabling controllable yeast-based production of lanostane triterpenoids with expanded structural diversity for more efficient than conventional artificial cultivation. Collectively, this work uncovers a non-canonical route for triterpenoid structural diversification beyond oxidosqualene cyclases, establishes a systematic strategy for deciphering biosynthetic pathways, and provides scalable, sustainable access to rare natural products.

An amphiphobic solvent, hexafluoroisopropyl methyl ether (FE), modulates Li+ solvation via a “relay push-escape” mechanism. After adding into a 1 M LiFSI-DME electrolyte, FE forces FSI− anions into the inner Li+ solvation sheath while expelling DME solvents, forming a CIP/AGG-rich structure. This confers the resulting electrolyte high ionic conductivity, a low melting point, weak solvation, and exceptional anodic/cathodic stability.

Lithium-metal batteries promise high-energy-density, wide operating temperature ranges, and fast charging. However, integrating these attributes remains a formidable challenge, as it necessitates an electrolyte that concurrently delivers high ionic conductivity, low solvation energy, low melting point, and the ability to form a stable electrode–electrolyte interphase (EEI), a feat elusive to conventional formulations. Here, we successfully address this challenge with a “relay push-escape” strategy using amphiphobic hexafluoroisopropyl methyl ether. Its anion-repulsive Coulombic field and steric hindrance transform conventional 1 M LiFSI-DME electrolyte into L4DF electrolyte, triggers a novel mechanism that drives anions into the inner Li⁺ solvation sheaths, displacing DME solvents to form a contacted ion-pair and aggregative ion-pair-dominated structure. The resulting L4DF electrolyte facilitates rapid Li⁺ desolvation and fosters the formation of a stable, anion-derived LiF-rich EEI. As a result, the L4DF electrolyte demonstrates exceptional compatibility with lithium-metal, showing high Coulombic efficiency of 99.7%. The LiNi0.8Co0.1Mn0.1O2||Li half-cell achieves 91.2% capacity retention after 1000 cycles and outstanding performance under 5 C fast-charging and low-temperature conditions. Remarkably, a 5.52 Ah pouch-cell reaches an energy density of 502.3 Wh kg−1 while retaining 87.6% of its capacity for 260 cycles. This work paves the way for the precise design of electrolytes for advanced batteries.

A side chain liquid crystal (LC) polymethylsiloxane (PMS) forms an unusual four-network gyroid (4NG) structure. In each of the two chiral subspaces, separated by the gyroid minimum surface, there are two networks of aromatic moieties instead of one. These wind around the central polysiloxane bundle, forming a double helix. Furthermore, the double helices are found to supertwist, their chiralities being opposite of those of the subspaces they occupy.

A liquid crystal (LC) polymethylsiloxane (PMS) with rod-like aromatic side-groups attached via an alkylene spacer and bearing three n-dodecyl end-tails is found to form an unusual cubic structure. In a normal LC double gyroid (DG), the two chiral subspaces, one each side of the G-surface, are occupied by one network each. Here each such network is split into two aromatic strands that wind around the central polysiloxane bundle, forming a double helix, resulting in a four-network gyroid (4NG). While in previous normal LC DGs the network twist was assumed to follow that of the subspace, in 4NG the twist sense of the double-helix is opposite to that of the subspace., i.e., while a right-handed subspace twists by +70.5° between junctions, the double-helix “supertwists” by −109.5°, and the opposite is true for the left-handed subspace. Detailed analysis by X-ray diffraction, DSC, and depolarized fluorescence (DF) shows a gradual but significant reversible change in the degree of mixing between the aromatic side groups and the polysiloxane backbones at 120 °C–130 °C in 4NG. Also, a significant increase in the system mobility starts only at ∼40 °C above the melting point, indicating persistence of local double-helical segments even in the melt.

A new class of highly selective artificial potassium channel has been developed by embedding 18-crown-6 ether ionophores into a polyimide scaffold via tunable alkyl linkers, achieving a remarkable K+/Na+ selectivity of 153.2 ± 5.3 along with high K+ conductance of 36.8 pS. This sets a new benchmark among synthetic channels and overcomes the classical trade-off between high ion conductance and selectivity.

Natural potassium channels such as KcsA exhibit extraordinary K+/Na+ selectivity (>1000), whereas the best biomimetic counterparts have reached only 41.3. To close this performance gap, we developed a modular design comprising three tunable components: a flexible aliphatic polyimide (PI) backbone, variable alkyl linkers (CnH2n+1, n = 4–16), and ion-binding 18-crown-6 units. This architecture promotes robust membrane integration via the PI scaffold and precise control of crown ether conformation and spatial arrangement through linker optimization, enabling exceptionally selective and efficient K+ transport. Of four synthesized polymer channels, three display high K+ conductance (36.8–47.0 pS) —up to twice that of gramicidin A (23.2 pS) —together with K+/Na+ selectivity exceeding 100. Notably, channel 4, incorporating the longest C16H33 linker, achieves an unprecedented selectivity of 153.2 ± 5.3. This synergistic combination of ultrahigh selectivity and superior conductance establishes a new benchmark for artificial potassium channels and provides a versatile platform for biomimetic membrane technologies, channel-targeted therapeutics, and biosensing applications.

A series of defect-tailored Cu3-based metal–organic frameworks (Cu3-MOFs) featuring coordinatively unsaturated Cu active sites were constructed for simultaneous direct air capture and photoreduction of CO2 to ethylene, offering fundamental insights for developing advanced materials in direct air-to-fuel conversion.

The development of efficient direct air capture (DAC) systems coupled with photocatalytic CO2 conversion is still an appealing challenge. Here, we engineered a series of defective Cu3-based metal–organic frameworks (Cu3-MOFs) for integrated atmospheric CO2 capture and in situ photoreduction. The defective Cu3-MOFs were constructed through selective removal of coordinated CO3 2− from pristine MOFs with HCl etching, generating unsaturated Cu active sites for CO2 harvesting, and the Cu3-MOFs demonstrated enhanced CO2 capture kinetics and capacity that compared to their pristine counterpart. Remarkably, the captured CO2 could be directly photoreduced to C2H4 with an optimal production rate of 18.25 µmol·g−1·h−1 without additional photosensitizer or sacrificial agent. The experimental and theoretical results revealed that the defective sites not only facilitated CO2 adsorption but also promoted C–C coupling of *CO intermediates, thereby enhancing C2H4 production. This work provides deep insights for designing advanced materials toward direct air-to-fuel conversion.

The reaction of K2Ge9(Hyp)2 (Hyp = Si(SiMe3)3) with phosphine stabilized silver halides gives the new intermetalloid cluster Ag12[Ge9(Hyp)2]6 exhibiting a novel Ag12 core surrounded by six [Ge9(Hyp)2] units acting as ligands. Within the Ag12 core two different kinds of silver atoms are present underlining the intermetalloid character of the cluster.

We present the synthesis and characterization of the novel intermetalloid cluster compound Ag12[Ge9(Hyp)2]6, exhibiting a silver core surrounded by bis-silylated Ge9-clusters. The new intermetalloid cluster has an Ag12 metal cluster core with silver atoms in different oxidation states. To the silver core six [Ge9(Hyp)2] units are coordinated, acting as ligands. The [Ge9(Hyp)2] units are arranged octahedrally around the Ag12 core, leading to a variety of Ag-Ge bonds and contacts. The cluster is a first example of an intermetalloid cluster, exhibiting a silver core, shielded by [Ge9(Hyp)2] units.

The local chemistry of individual Ti3C2T x MXene flakes and confined water are investigated by in situ Scanning Transmission X-ray Microscopy (STXM) in aqueous environment. We reveal water-induced redox reactions non-uniformly distributed over the MXene flakes upon sequential exposure to acidic and neutral aqueous solution containing alkali cations.

Water at an interface, confined in nanopores or between layers exhibits unique structural and dynamic properties that differ significantly from bulk water. In layered 2D materials such as MXenes, intercalated water is believed to affect their surface chemistry by inducing local oxidation and contribute to redox processes during electrochemical cycling. However, the chemical nature of confined water and its interaction with MXene surface chemistry remains unclear. Here, we employ scanning transmission X-ray microscopy (STXM) to investigate in situ the chemical interaction of water in individual Ti3C2T x MXene flakes in humid and aqueous environments with ∼50 nm spatial resolution. At the oxygen K-edge, we uncover that water trapped in pockets and wrinkles in few-layered MXene flakes has a different hydrogen bonding compared to water confined in the MXene interlayer spacing. We also reveal water-induced local redox reactions of Ti atoms non-uniformly distributed on the MXene flake upon interaction with liquid water and alkali ion neutral electrolytes, which are partly reversible upon exposure to an acidic electrolyte.

Anodic oxidation unlocks C─N bond formation in electron-rich fluoroarenes. Spatial separation of redox events extends the lifetime of active intermediates, expands the scope of nucleophilic aromatic substitution reactions, and promotes a new mechanism for SNAr reactions: uphill redox catalysis. Powered by voltage control, azolation occurs quickly and selectively; reactions proceed with catalytic charge and can be easily scaled in a batch setup.

Nucleophilic aromatic substitution (SNAr) reactions are critical methods for forming C─N bonds in synthetic campaigns, but limitations in electrophile electronics restrict access to a large portion of chemical space. Photochemical oxidation of fluoroarenes has emerged as an attractive strategy to activate fluoroarenes toward nucleophilic addition, but back-electron transfer to solution-phase reduced photocatalysts limit the scope and efficiency of these methods. Herein, we describe an electrochemical strategy to overcome this obstacle by spatially separating redox events at electrode surfaces, extending the lifetime of the activated electrophile and enabling the azolation of electron-rich alkoxyfluoroarenes. Through stabilization of the oxidized product with voltage control and HFIP solvent, the reaction proceeds with catalytic charge via a proposed uphill redox chain mechanism. A wide range of electron-rich fluoroarenes and azoles are tolerated—including those with orthogonal functional group handles. The redox catalytic nature of this e-SNAr reaction enables energy and mass efficient syntheses and facile scaling in a simple batch setup.

Herein, a series of phosphorescence films were achieved by boron hybridization engineering, with the longest phosphorescence lifetime reaching up to 2.23 s under ambient conditions. Notably, the formation of B-N bonds can not only reduce the vibrational of triplet excitons, but also act as stimulus-responsive sites, which undergo cleavage and formation under the stimulation of acids and bases.

Organic room temperature phosphorescence (RTP) materials have attracted widespread attention for their potential in both fundamental research and advanced technologies. However, their development is hindered by weak spin-orbit coupling and nonradiative decay. Here, we present a boron hybridization engineering strategy in which arylboronic esters are incorporated into poly(4-vinylpyridine). By regulating the hybridization state of boron atoms from sp 2 to sp 3, the phosphorescence properties can be effectively tuned. Simultaneously, the formation of B-N bonds suppresses nonradiative decay, leading to long-lived RTP with lifetimes up to 2.23 s. Both experimental evidence and theoretical calculations confirm the occurrence of boron hybridization switching and its decisive role in modulating phosphorescence. Moreover, the B-N bonds exhibit acid-base responsiveness, endowing the system with dynamic phosphorescence behavior. Beyond demonstrating triplet exciton control, this work establishes a molecular design principle that may guide the creation of multifunctional organic phosphorescent materials.