The trifluoromethoxy group features high electronegativity and strong lipophilicity, making it a valuable substituent in drug discovery and materials science. To fully elucidate its function, the efficient preparation of stereodefined analogues is essential. The established dehydroxytrifluoromethoxylation reaction, while synthetically useful, follows an S_N1 mechanism and consequently produces racemic products. Herein, we report a stereospecific S_N2 dehydroxytrifluoromethoxylation reaction of alcohols using commercially available and low-cost 2,4-dinitro(trifluoromethoxy)benzene (DNTFB) as the trifluoromethoxide source. The reaction employs fluoro-N,N,N',N'- tetramethylformamidinium hexafluorophosphate (TFFH) as a dual activator, which both activates the alcohol toward isouronium formation and provides a fluoride ion to liberate the CF₃O^- anion from DNTFB. Under mild conditions, a range of primary and secondary alcohols undergo efficient conversion with excellent functional group tolerance. Notably, enantioenriched secondary alcohols react with complete configurational inversion, confirming the S_N2 pathway. The synthetic utility is further demonstrated by gram-scale synthesis and functionalization of complex bioactive molecules. This stereospecific method offers a highly efficient, low-cost, and broadly applicable strategy for the late-stage modification of complex drug molecules, providing a practical entry to optically pure alkyl trifluoromethyl ethers.

The development of photoresists that combine high-sensitivity with environmental benignity is essential for advancing next-generation nanofabrication technologies. Herein, we present a molecular engineering strategy wherein selenite ligands are employed to assemble a series of dinuclear phenylantimony(oxo)-selenite clusters (designated as α, β, γ) with precisely tunable phenyl group densities, ranging from four to eight per cluster. A synergistic sensitivity mechanism is elucidated: the high-atomic-number (Z) inorganic core, comprising Sb and Se, functions as an efficient energy absorption antenna, while the surrounding shell of labile Sb–C bonds gives a high density of reactive initiation sites. Among the series, cluster γ exhibits optimal lithographic performance, achieving complete solubility switching at 26 μC·cm^–2, while maintaining sub-nanometer film smoothness. Notably, all resists are fully developable in pure water, underscoring their compatibility with environmentally sustainable processing. This work establishes a synergistic core-shell design principle for the development of high-performance, eco-friendly photoresists.

The rapid advancement of organic mixed ionic-electronic conductors (OMIECs) has driven steady improvements in organic electrochemical transistor (OECT) performance. However, achieving an optimal balance between charge-carrier mobility (μ) and volumetric capacitance (C*) remains a fundamental challenge, particularly when relying on chemical copolymerization strategies to fine-tune glycolated side-chain content. Such approaches are often hindered by synthetically demanding routes and pronounced batch-to-batch variability, which impede the establishment of robust structure-property relationships. Herein, we introduce a physical blending strategy: glycolated and alkylated donor-acceptor (D-A) polymers are blended across a compositional gradient to yield a series of films with systematically varied hydrophilic/hydrophobic side-chain ratios. We comprehensively investigate how the blend ratio governs electrochemical doping kinetics, nanoscale film morphology, and OECT device metrics. Critically, varying the glycolated/alkylated polymer ratio induces continuous, nanoscale phase separation, yielding a morphologically integrated dual-channel architecture that simultaneously facilitates ion transport through hydrophilic domains and electron transport through interconnected hydrophobic pathways. Importantly, this physical blending approach circumvents the synthetic complexity of copolymer design, enabling precise, modular tuning of side-chain composition and device optimization using only two well-defined parent polymers. Our strategy thus establishes a scalable, reproducible, and highly tunable approach for engineering high-performance OECT channel materials.

Nitrene-mediated S–H/O–H insertion reactions serve as a core strategy for constructing value-added N–S/N–O bonds, which are indispensable motifs in pharmaceuticals, functional materials, and agrochemicals. However, traditional approaches are plagued by intractable issues: severe side reactions (e.g., Curtius rearrangement), harsh reaction conditions, and transition-metal catalyst deactivation caused by strong coordination of thiols/alcohols. Herein, we report a metal-free photochemical protocol using dibenzothiophene sulfilimines as nitrene precursors, triggered by 365 nm LED irradiation at room temperature. Simple additives (2-amino-4-chlorobenzoic acid) play dual pivotal roles: mediating triplet energy transfer to activate sulfilimines and acting as proton donors to suppress side reactions. Comprehensive mechanistic studies (radical capture experiment, EPR, nanosecond transient absorption spectroscopy, and DFT calculations) confirm singlet nitrene as the key reactive intermediate for the dominant pathway, while a triplet nitrene-mediated radical-radical cross-coupling mechanism is also feasible for thiol substrates. This protocol features broad substrate compatibility, scalable synthesis without yield loss, and validated synthetic utility, providing a practical avenue for efficient N–S/N–O bond formation.

Solution-processable organic photovoltaic (OPV) cells show promise for industrialization; however, high-performance polymer donors often rely on costly fused-ring structures. Here, we propose a novel polymer donor, 4T-Pz, which is a low-cost, fully non-fused donor featuring a pyrazine-based structure. Benefiting from the energy-level modulation induced by pyrazine units and enhanced backbone planarity, 4T-Pz exhibits a deep HOMO level (–5.38 eV), pronounced solution-state pre-aggregation, and favorable molecular packing behavior, thereby facilitating efficient charge generation and transport. When blended with two non-fused acceptors, A4T-16 and TBT-26, to form fully non-fused active layers, the optimized OPV cells deliver power conversion efficiencies of 14.2% and 12.7%, respectively. The 4T-Pz:A4T-16 system shows superior performance due to lower energy loss, weaker trap-assisted recombination, a uniform fibrous film morphology, and compact face-on π–π stacking, which favors charge transport. Cost analysis confirms competitiveness of 4T-Pz, with materials-only cost (MOC) of 11.63 USD·g^–1, far lower than that of fused-ring analogs. This work demonstrates the promise of pyrazine-based fully non-fused polymer donor in balancing performance and cost, and provides a viable materials-design route toward scalable, high-efficiency OPVs.

The inherent polarity mismatch suggests that direct α-nucleophilic addition is disfavored both thermodynamically and kinetically under conventional conditions. However, indirect α-nucleophilic addition reactions of α,β-unsaturated carbonyl compounds via copper-catalyzed radical pathways have been well established. Herein, we reported a formal asymmetric α-nucleophilic addition reaction of α,β-unsaturated carbonyl compounds through merging photoredox catalysis with copper catalysis. This transformation proceeds via radical addition to an α,β-unsaturated carbonyl compound, followed by a C–O bond cross-coupling reaction to afford the corresponding chiral γ-lactones. With this strategy, a diverse range of chiral γ-lactones bearing a quaternary stereocenter could be afforded.

Sulfonyl and sulfonimidoyl fluorides serve as versatile SuFEx hubs for forming diverse bonds at the S(VI) center, with applications in medicinal chemistry, chemical biology, and materials science. Their state-of-the-art synthesis via modular fluorosulfonylation and fluorosulfonimidation typically relies on the use of acidic fluoride salts and suffers from slow reaction kinetics, primarily due to the intermediacy of the widely adopted S(VI)-DABCO adducts generated through redox processes. On the other hand, aryl thiophenium salts have been recognized in energy transfer catalysis for their ability to generate aryl radicals and thiophenium radical cations, a reactivity profile that has been exploited in radical coupling with ethylene. Despite this promise, their application in other radical-radical coupling manifolds remains underexplored. Herein, we report a highly efficient radical-radical cross-coupling strategy for assembled fluorosulfonylation and fluorosulfonimidation with aryl thianthrenium salts using cesium fluoride under energy transfer catalysis. The substantial advances stem from the energy transfer process that generates the persistent thianthrenium radical cation and subsequently results in formation of the key highly electrophilic S(VI)-thianthrenium species, which have enabled fast reaction kinetics with broad functional group tolerance. Mechanistic studies provided compelling evidence for the proposed pathway: the aryl radical was intercepted by TEMPO and BHT, while the pivotal S(VI)–thianthrenium intermediate was directly detected by high-resolution mass spectrometry. The reaction can be easily scaled up and readily applied for late-stage functionalization. To be noted, our strategy allows, for the first time, highly regioselective fluorosulfonimidation of aromatics with fluoride. The exceptional regiochemical outcome is attributed to the inherent site selectivity of the thianthrenation step, combined with the superior reaction kinetics imparted by the highly reactive S(VI)-thianthrenium intermediates. Both the resulting sulfonyl fluorides and sulfonimidoyl fluorides undergo SuFEx reactions smoothly under mild conditions, providing rapid access to complex molecules with diverse S(VI)-functional groups.

The unique combination of solution processability, modular synthesis, and post-synthetic modification (PSM) capabilities renders metal–organic cages (MOCs) a highly promising platform for diverse applications. In this work, a pair of pure enantiomers, PTC-377(Λ,S) and PTC-377(Δ,R), were synthesized via selective coordination of π-conjugated chiral cations, [Ag₂(1S,2S-DPEN)(DPPM)]²⁺ and [Ag₂(1R,2R-DPEN)(DPPM)]²⁺, to the vertices of racemic ΔΔΔΔ- and ΛΛΛΛ-Zr₄L₆ (L = embonate) cage precursors, respectively. The chiral resolution and surface modification of the zirconium cage result in a pronounced circularly polarized luminescence (CPL) response. Furthermore, the loading of π-conjugated 1,10-phenanthroline (phen) within the mesoporous channels of PTC-377 yields the composite phen@PTC-377. Thin films of this composite exhibit a dramatically enhanced optical limiting effect, with the normalized transmittance minimized at 0.11—a significant improvement over both the pristine Zr₄L₆ cage (~1) and the parent PTC-377 (~0.65). According to theoretical calculations, the enhanced optical limiting effect originates from the strong π–π stacking at the edge site between phen and the PTC-377 framework, these interactions extend the conjugated system and facilitate efficient charge transfer, thereby enhancing the polarizability and hyperpolarizability of the molecule.

Reversible control of topology and partial-interpenetration transformations in metal-organic frameworks (MOFs) is vital for customizing their functional properties, but this area has long been insufficiently explored. Herein, we report the reversible regulation of both topology and partial-interpenetration in photo/thermal-responsive MOFs, focusing on the two-interpenetrated [Zn(L₁)(H₂O)]_n (L₁ = biphenylethene-4,4'-dicarboxylic acid). Through solid-state [2+2] cycloaddition reactions, this MOF was transformed into partially interpenetrated [Zn(L₁)_x(L₂)_1–x(H₂O)]_n (x represents the molar ratios of organic linkers) and non-interpenetrated [Zn(L₂)(H₂O)]_n with different topology (L₂ = 4,4',4”,4”'-(cyclobutane-1,2,3,4-tetrayl)tetrabenzoic acid, a cyclobutane derivative of L₁), and thermal treatment triggered reverse ring-opening to recover the original structure. These transformations were verified and visualized using single-crystal X-ray diffraction, synchrotron infrared spectroscopy, and other techniques. By introducing a third organic linker L₃ (azobenzene-4,4'-dicarboxylic acid), we synthesized multivariate MOFs (MTV-MOFs, [Zn(L₁)_x(L₃)_1–x(H₂O)]_n) and precisely tuned their structural transformations by adjusting the ratio of the two linkers. By leveraging the inherent photoactivity of these MOFs and the photoexcited electrons generated during these structural transformations, they can be used to detect reductive molecules such as glucose. Their photocurrent-based glucose detection exhibited a high sensitivity of up to 780 μA·M^–1·cm^–2. This work enriches the structural diversity of MOFs and enhances their potential applications in adsorption and molecular recognition.

All-carbon quaternary stereogenic center is a valuable structural motif, which is widely present in natural products and pharmaceutical candidates. Therefore, the development of straightforward and efficient methods for the synthesis of all-carbon quaternary stereogenic center is of great significance. Herein, we report a copper-catalyzed remote asymmetric yne-allylic substitution to construct adjacent chiral centers bearing an all-carbon quaternary stereocenter. The use of readily available starting materials, the mild reaction conditions, high yields, excellent enantioselectivities, and a broad substrate scope, underscore its practicality and synthetic utility of this method.

Alkenyl allenes represent a privileged subclass of allenes; the conjugation between the cumulated diene and the adjacent alkenyl group imparts distinctive chemical behaviors, rendering them valuable precursors for complex molecular architectures via transformations such as Diels–Alder cycloadditions and Nazarov cyclizations. Palladium-catalyzed β-hydride (β-H) elimination represents a fundamental and well-established strategy in organic synthesis, extensively utilized for the preparation of allenoates and aryl allenes. However, extending this powerful transformation to the synthesis of conjugated alkenyl allenes has historically proven to be a formidable challenge. This synthetic difficulty arises primarily from the intrinsic thermodynamic instability of the alkenyl allene motif, which is notoriously prone to rapid isomerization into more stable conjugated polyenes, often resulting in complex mixtures of byproducts and preventing the isolation of the desired compound. To address this long-standing limitation and achieve high selectivity, we herein report a robust and highly efficient protocol for the selective synthesis of alkenyl allenes via the Pd/Xu-Phos-catalyzed β-H elimination of 1,3-dien-1-yl triflates. Central to the success of this method is the identification and application of the sterically tuned Xu-Phos ligand. This bulky, electron-rich phosphine ligand effectively facilitates the challenging elimination step, while simultaneously suppressing the competitive hydropalladation and subsequent isomerization pathways that have plagued previous attempts. The reaction is proposed to proceed through an acetate-assisted intramolecular deprotonation manifold. Consequently, this methodology features exceptionally mild reaction conditions and demonstrates broad functional group compatibility. It provides general access to diverse di- and trisubstituted alkenyl allenes in high yields and excellent selectivities. These products serve as pivotal precursors for the construction of complex bicyclic scaffolds via subsequent cyclization reactions, thereby opening new avenues for the synthesis of bioactive natural products and pharmaceuticals.

Ru(I) radicals with a 4d⁷ electronic configuration are sought after for their unique electronic structure and synthetic utility in chemical transformations. However, due to their high reactivity, ligand scaffolds effecting the stabilization of Ru(I) species are exceedingly rare. In this study, we present readily accessible, persistent Ru(I) radicals supported by N-heterocyclic carbenes (NHCs) and p-cymene, [RuCl(NHC)(η⁶-p-cymene)]. These halide complexes are easily prepared via single-electron reduction of their Ru(II) dichloride precursors. Integrated single-crystal X-ray diffraction, EPR spectroscopy, magnetic measurements, and DFT studies establish an S = 1/2 ground state with spin density primarily localized on ruthenium. Frontier molecular orbital analysis indicates that the stabilization of these Ru(I) radicals originates from the synergistic interplay of the strong σ-donation from the NHC ligand and δ-acceptance of the arene ligand. Accordingly, voltammetry study showes a reversible one-electron oxidation at relatively high potential (E_1/2 = –0.32 V vs. SCE) and an irreversible one-electron reduction at very low potential (E_p = –2.17 V vs. SCE). Furthermore, the chloride ligand in these Ru(I) complexes allows chloride-to-phosphine exchange reaction as demonstrated by the preparation of the cationic Ru(I) complex [Ru(PMe₃)(IMes)(η⁶-p-cymene)][BPh₄] from the reaction of [RuCl(IMes)(η⁶-p-cymene)] with PMe₃ and NaBPh₄, underscoring their utility as tunable precursors for catalysis.

Chiral 1,4,5,6-tetrahydropyridazine core has emerged as valuable structural motifs in drug discovery, and has been recognized that the identified stereocenter of this structure has a significant impact on activity. Nevertheless, the catalytic asymmetric synthesis of such frameworks with clearly defined stereocenters remains a significant challenge, primarily due to the inherent difficulty in achieving stereo control during the cyclization process, as well as the limited availability of broadly applicable efficient catalytic system. In this work, a novel palladium-catalyzed enantioselective aminoalkenylation and aminoarylation of γ,δ-unsaturated hydrazones with aryl or alkenyl halides is described. The use of a sterically demanding Xu-Phos ligand ensures excellent chemoselectivity and enantioselectivity. This protocol provides an efficient and practical strategy for the synthesis of structurally diverse chiral tetrahydropyridazines bearing alkenyl and aryl functionalities in good yields and high enantioselectivities under mild reaction conditions. Notably, preliminary mechanistic investigations indicate that the syn-azapalladation was found to be the dominant pathway and might elucidate the high enantioselectivity in the cyclization process.

Vicinal diamines, recognized for their attractive structural motifs and functional versatility, are widely used in pharmaceuticals, catalysis and functional materials. As the best choice, the diazidation of alkenes offers an efficient route for the rapid decoration of diazide compounds, which can be converted to the corresponding diamines via a simple reduction step. Although advanced strategies for alkene diazidation, primarily involving radical ligand transfer or a combination of radical ligand transfer and ligand-to-metal charge transfer, have been developed, most of the methods still face some limitations, such as the requirement for superstoichiometric oxidants, and notably differ substantially in substrate applicability. To address this shortcoming, we combine IBA-N₃ with in-situ generated Mn^II-N₃ to establish a synthetic strategy that can cover most of the different known pathways to incorporate the azide group into diazide compounds. Consequently, this protocol can significantly increase the suitable range of alkenes by overlapping multiple pathways to obtain azide sources. Mechanistic analysis indicates that this transformation strategy can include redox, photochemical homolysis of I^III-N₃, radical ligand transfer and radical group transfer processes to form a practical design to achieve alkene diazidation with a better scope of alkene tolerance.

Triarylmethyl radicals are representative carbon-centered open-shell species whose persistence and reactivity are highly sensitive to molecular structure. Incorporation of an anthracene unit offers an attractive strategy for stabilizing such radicals because its extended π-framework can promote spin delocalization while simultaneously providing steric protection. However, spin delocalization onto the anthracene framework may also generate coupling-prone peripheral sites, making the resulting radicals susceptible to dimerization and photodegradation. Herein, we systematically investigate how para-substitution on the anthracene unit governs the radical fate of anthracene-substituted bis(2,4,6-trichlorophenyl)methyl radicals. A series of derivatives bearing no substituent, a triisopropylsilylethynyl group, a 4-tert-butylphenyl group, or a mesityl group at the anthracene para-position were prepared and compared. Strikingly, different outcomes were observed after oxidation. The unsubstituted system undergoes direct intermolecular coupling followed by further oxidation to afford quinonoid closed-shell dimer 2C. Introduction of a triisopropylsilylethynyl substituent enables formation of radical 4R in solution, but crystallization induces irreversible σ-dimerization to give 4D. The 4-tert-butylphenyl-substituted radical 5R exhibits improved but still limited persistence. In contrast, the para-mesityl-substituted derivative 6R can be isolated as a persistent radical and structurally characterized by single-crystal X-ray diffraction. Combined crystallographic, UV–vis, EPR, electrochemical, and theoretical studies reveal that these divergent outcomes originate from the interplay between spin-density redistribution and local steric shielding at the coupling-prone anthracene para-position. Consistently, the photostability of the radicals increases progressively from 4R to 5R and 6R, with half-lives of approximately 57, 79, and 222 min, respectively, under continuous 365 nm irradiation. This work establishes para-substituent engineering as an effective strategy for controlling dimerization versus persistence in anthracene-substituted triarylmethyl radicals and provides a useful design principle for persistent π-conjugated carbon-centered radicals.

Mechanical interlocking has recently emerged as a novel structural design principle for crystalline porous organic materials. Unlike traditional reticular chemistry that relies on covalent or coordination bonding to build rigid lattices, mechanical bonding provides an alternative design space where the structural integrity of the crystal is maintained while the individual components preserve intrinsic mobility. The incorporation of interlocked macrocycles, cages, and framework subunits has enabled new forms of structural order that combine crystallinity with dynamic molecular motion. This review summarizes current progress in the synthesis and structural design of crystalline porous materials driven by topology interlocking. The discussion is organized by increasing structural hierarchy, covering interlocked macrocycles, interlocked cages, mechanically interlocked metal-organic frameworks, and interlocked covalent organic frameworks. The relationships between interlocking geometry, structural organization, and application area are highlighted. The review concludes with an outlook on the opportunities and challenges associated with mechanical bonding as a programmable element in crystalline porous materials.

A brief overview of the leading contributors in the field highlights how topology interlocking has become a powerful design principle for crystalline porous materials. Foundational insights were provided by Sauvage and Stoddart in the 1980s, whose studies on mechanically bonded molecules and molecular machines significantly promoted the development of mechanically interlocked molecules. Fujita advanced the field by showing that metal-directed self-assembly can spontaneously produce catenated metal-organic cages (MOCs) and macrocycles, while Cooper demonstrated that catenated organic cages can arise through dynamic covalent chemistry without metal templates. Mechanical interlocking was extended to frameworks by Yaghi, who realized woven covalent organic frameworks (COFs), and by Loh, who introduced rotaxane-based COFs with engineered interlayer behavior. Aida and Sato reported the first metal-organic frameworks constructed from a catenated polymer backbone. Most recently, Cui and co-workers first reported an interlocked metal peptide macrocycle and hetero-interlocked MOC. Important contributions from Jin and Guido Clever expanded the scope of interlocked macrocycles and MOCs, respectively. Collectively, these achievements established the foundation of topology interlocked crystalline porous materials.

The sustainable electrochemical conversion of inert small molecules, such as N₂, CH₄, and CO₂, is opening new frontiers in green chemistry and energy technologies. Each of these molecules can be individually converted into a valuable chemical, offering the potential to replace existing industrial processes. Electrochemical N₂ reduction to NH₃ could replace the Haber-Bosch process, avoiding the high-temperature and high-pressure conditions. Beyond NH₃, N₂ fixation is expanding toward diverse nitrogen-containing chemicals. The catalytic oxidation of CH₄ is referred to as the “Holy Grail” reaction, as it is difficult to activate the first C–H bond and control the product selectivity. Nevertheless, CH₄ oxidation under mild electro/photo-electrochemical conditions enables the facile activation of the inert C–H bond, and the selectivity can be efficiently adjusted by exquisitely designing the electrode interface. Electrocatalytic CO₂ reduction is a key technology for achieving carbon neutrality. Currently, the reaction continues to advance from mono-carbon toward multi-carbon products with improved activity and stability. In addition to the individual conversion of these inert small molecules, intermolecular coupling reactions such as C–N coupling reaction between N₂ and CO₂ provide further opportunities for electrochemical reactions. Collectively, these efforts represent a paradigm shift from fossil-based processes toward scalable, eco-friendly pathways for value-added chemicals.