This study leverage microemulsion engineering to achieve compatibility of propylene carbonate (PC)/graphite (Gr) system. Insoluble glyceryl monostearate (GMS) and amphiphilic tetrahydrofuran (THF) self-assemble into core-shell micelles in the PC electrolyte medium. At the Gr anode, adsorbed GMS@THF micelles create a solvophobic barrier and effectively suppress the Li+-PC co-intercalation. This design enables Gr||LiFePO4 batteries operate from −60 °C to 100 °C, providing a novel strategy for incompatible electrolyte/electrode systems and all-climate batteries.

Propylene carbonate (PC)-based electrolytes are promising for all-climate lithium-ion batteries due to their wide liquid range. However, detrimental Li+-PC co-intercalation causes severe graphite (Gr) anode exfoliation, remaining the biggest barrier for their practical application. Although the issue can be mitigated via solvation regulation, complex interfacial chemistry limits long-term cycling ability. Herein, we designed a PC-based microemulsion electrolyte to achieve PC/Gr compatibility through interfacial manipulation. Specifically, insoluble glyceryl monostearate (GMS) and amphiphilic tetrahydrofuran (THF) are introduced into the PC-based electrolyte. GMS self-assembles in THF to form core-shell GMS@THF micelles dispersed in the continuous PC electrolyte medium. This microemulsion structure generates abundant liquid-liquid interfacial tension at micelle/electrolyte interfaces, spontaneously directing micelles to the electrode interfaces during operation. At the Gr anode, adsorbed GMS@THF micelles leverage solvophobic effects to synergistically form PC-poor Li+ solvation sheaths and block free PC, effectively suppressing detrimental PC co-intercalation. This design enables Li||Gr cells achieve a high initial Coulombic efficiency of 92.8% and supports 1 Ah Gr||LiFePO4 pouch cells to operate over 4000 cycles. Remarkably, the pouch cells work well across extreme temperatures (−40∼100 °C cycling; −60∼100 °C operation), demonstrating exceptional all-climate capability. This microemulsion engineering establishes a universal paradigm for optimizing electrolyte/electrode interphases in the PC/Gr system.

The excessively required pressure for pressure-driven irreversible emission transformation significantly inhibiting practical applications. Here, we achieved an irreversible emission transformation in zero-dimensional (TPA)CuI2 NCs (TPA = Tetrapropylammonium) via high pressure engineering, even at pressure as low as 0.6 GPa. Furthermore, (TPA)CuI2-PVA films can be utilized in flexible pressure imaging by stamping or writing. Different recovery time upon applying different pressures provides dynamic passwords and time-sensitive intelligence, thus eliminating the false and retaining the true.

Pressure-driven irreversible emission transformation as an efficient means greatly facilitates the development of the rational structural design of high performance novel metastable states. However, the excessively required pressure can only be achieved by high-pressure devices, significantly inhibiting practical applications. Here, we achieved an irreversible emission transformation in 0D copper halides (TPA)CuI2 (TPA = Tetrapropylammonium) nanocrystals (NCs) via high pressure engineering, even at pressure as low as 0.6 GPa (approximately 6000 atmospheres). The large steric hindrance of organic cations (TPA+) and enhanced hydrogen bonding increased the potential barrier of phase transition, resulting in an irreversibility. The quenched samples exhibited bright green emission after pressure treatment, greatly different from the initial dull white light. The (TPA)CuI2 NCs-based film can be utilized as flexible and water-resistant pressure imaging that just required macroscopic pressure, such as stamping or writing. Furthermore, the different recovery time upon applying different pressures provides dynamic passwords and time-sensitive intelligence——eliminating the false and retaining the true. This work develops a promising pressure-sensing material which can be easily accessible in practical applications for schlagstelle inspection of pipeline inwall and anti-counterfeiting.

A device-level diagnostic study reveals that RuOx anodes in PEMWE suffer from irreversible loss of bridging oxygen (Obridge), leading to deactivation. The Ru–O stabilization strategy was proposed by low-level Ir doping to suppress Obridge loss, which maintains stable ampere-level operation. This work links atomic-scale structural dynamics to performance loss, which establishes a new paradigm for diagnosing under real PEMWE conditions.

Ruthenium oxide (RuO x ) is a promising anode catalyst for proton exchange membrane water electrolysis (PEMWE), but its degradation mechanism, especially under practical ampere-level operation, remains elusive. Herein, we established a device-level diagnostic framework to investigate the evolution of RuO x . Operando PEMWE-based X-ray absorption spectroscopy (XAS) revealed a progressive negative shift of the Ru K-edge. Extended X-ray absorption fine structure (EXAFS) analysis further showed a pronounced decrease in both Ru–O and Ru–O–Ru coordination, revealing that irreversible loss of bridging oxygen (Obridge) triggers the final catalyst deactivation. Guided by these insights, we demonstrated that low-level Ir doping in Ru0.9Ir0.1O x could notably increase the Obridge vacancy formation energy and thus stabilize the Ru–O framework. Under identical PEMWE operating conditions, the Ru valence state and coordination environment in Ru0.9Ir0.1O x remain relatively stable. In-cell electrochemical impedance spectroscopy (EIS) and distribution of relaxation time (DRT) analyses confirmed that this structural stabilization strategy effectively maintains low electrode kinetic and proton transport resistances across a range of cell voltages, enabling stable operation at industrially relevant ampere-level current densities. Finally, the resulting Ru0.9Ir0.1O x catalyst achieves 1.74 V at 3 A cm−2 and stably operates for 500 h at 1 A cm−2, outperforming most reported Ru-based anodes.

The newly discovered CuGe2Se3 adopts a layered structure with surprisingly short Cu─Ge and Ge─Ge contacts, characterized by single-crystal X-ray diffraction (SCXRD) and solid-state (SS) NMR. Electronic structure analysis rationalizes the stability of this unique structural framework. CuGe2Se3 exhibits promising thermoelectric (TE) performance, with a high Seebeck coefficient (∼374 µV·K−1) and ultralow thermal conductivity (∼0.35 W·m−1K−1) at 755 K.

Unraveling the relationship between thermodynamic factors, interatomic interactions, and electronic structure remains a crucial yet elusive challenge in the discovery of novel materials in solid-state (SS) chemistry. In the quest for new thermoelectric (TE) materials, we overcame that fundamental problem for the case of CuGe2Se3, whose synthesis, unique crystal structure, and transport properties are reported herein. The giant two-dimensional (2D) structure of CuGe2Se3, consisting of Se/(Cu─Ge)/Se and Se/(Ge─Ge)/Se slabs stacked along the c-axis, exhibits short Cu─Ge and Ge─Ge interactions, as evidenced by single-crystal X-ray diffraction (SCXRD) and SS NMR spectroscopic studies. These homopolar bonds might be surprising, as such interactions are rarely observed in group IV-chalcogenides. The compound is thermally stable up to ∼823 K. Transport properties measurements revealed a high Seebeck coefficient (∼373.6 µV·K−1) and ultralow thermal conductivity (∼0.35 W·m−1K−1) at 755 K, ascribed to its weak bonding interactions. We followed up with a theoretical analysis to gain insight into its structural peculiarities, focusing on vibrational properties and the nature of chemical bonding. The formation of Ge─Ge bonds is favored in light of the presence of multicenter bonds, which receive contributions from stereochemically non-active Ge lone pairs.

This work presents the first Sorp-vection-based membrane separation for silicone oil purification, coupling sorption-driven selectivity with convective transport. Our strategy enables highly selective removal of residual cyclic siloxanes, particularly D4, overcoming the inherent trade-offs and limitations associated with conventional membrane processes in the silicone industry.

“Sorp-vection” is a membrane separation technique that synergistically combines sorption with convective flow mechanisms. Beyond its conceptual discussion, we demonstrate a sorp-vection separation achieved in a gas–liquid system, where permeation of a gas directly drives selective permeation of an organic solute across a dense polymer layer overcoming osmotic limitations of conventional membrane processes. Here, a long-standing challenge in silicone oil production is addressed, in which residual cyclic oligosiloxanes are removed from silicone oil streams through permeation of CO2 across an optimally crosslinked PDMS selective layer. A lab-scale 1st generation Sorp-vection system demonstrated, with a separation factor above 15 to remove D4 (octamethylcyclotetrasiloxane) from low-concentration feeds using both lab-grade silicone oil (Sigma-Aldrich) and an industrial-grade feed (DOW-SFD). Good agreement was found with a predictive model based on liquid D4 and high-molecular-weight silicone oil sorption data in crosslinked PDMS. This proof-of-concept study introduces the sorp-vection strategy, expanding it from conventional two-component systems to a three-component configuration in which convective flow is introduced as an independent driving entity. Addressing concentration polarization in next-generation versions of the sorp-vection process is expected to ensure stable long-term performance and to establish sorp-vection as a transformative approach for industrial purification.

A metal-free nitrosation process enables direct C–H functionalization of polyethylene (PE) with high selectivity, producing either oxime- or carbonyl-functionalized polymers. Using t-BuONO under visible light or thermal conditions, the process operates in both lab-scale and industrial settings. The resulting oxime groups serve as versatile intermediates, enabling scalable and sustainable PE upcycling.

Polyethylene (PE), the world's most produced synthetic polymer, is highly durable but resistant to chemical modification due to its inert carboncarbon backbone. This work presents a metal-free, nitrosation process for direct CH functionalization of PE, enabling selective formation of oxime- or carbonyl-functionalized polymers. The method operates under mild visible-light conditions in solution and through thermally driven reactive extrusion, making it suitable for both laboratory and industrial applications. The key reagent, tert-butyl nitrite (t-BuONO), produces an alkoxy radical (t-BuONO•) for CH activation and a persistent nitrosyl radical (NO•) that installs ketoxime functionalities. Mechanistic studies using quantum yield determination and time-resolved transient absorption spectroscopy confirm the energy-transfer activation of t-BuONO and hydrogen atom transfer pathways. Unlike previous strategies, this approach yields pure oxime or keto-functionalized PE's without metals or pre-functionalization. Moreover, oxime groups serve as intermediates convertible into esters, ethers, or urethanes, allowing control over polymer polarity and thermomechanical properties. Together, this strategy transforms a venerable small-molecule transformation into a scalable, selective, and tunable route for the upcycling of PE, and enables a selective and sustainable route to valorize one of the world's most ubiquitous, but most recalcitrant plastics.

This work presents a self-sustaining catalytic membrane that harnesses pollutants as electron donors to drive oxygen activation. This autonomous paradigm leverages the inherent chemical energy of wastewater, thereby eliminating chemical additives and reducing energy consumption compared to conventional UV- or electrochemical-based systems.

Conventional catalytic water purification remains energy- and chemical-intensive due to reliance on external stimuli for oxidant activation. Here, we present a self-sustaining catalytic membrane (TMF-CM) incorporating Ti-doped Mn3O4/Fe3O4 catalysts with engineered oxygen vacancies, which harness pollutants as electron donors to drive enzyme-mimetic redox cycles. Through nanoconfinement within ceramic membrane pores, dissolved oxygen is autonomously activated by electrons derived from contaminants, enabling continuous regeneration of active sites without chemical additives. Mechanistic investigations, supported by spectroscopic and computational evidence, reveal that high-valent metal–oxo intermediates mediate contaminant oxidation while concurrently restoring oxygen vacancies, thereby sustaining catalytic cycles. During 10-day continuous testing in real wastewater, the TMF-CM system achieved over 90.1% contaminant removal and exhibited self-cleaning capability. This autonomous catalytic paradigm leverages the inherent chemical energy of wastewater, eliminating chemical additives and cutting energy consumption by 70%–98% compared to UV- or electrochemical-based systems. By integrating molecular oxygen activation with circular electron transfer, we establish a sustainable oxidation strategy that extends beyond conventional water treatment paradigms.

The dual-site synergistic interface promotes interfacial charge redistribution on the catalyst surface, achieving efficient and highly selective photo-reforming of waste plastic into acetic acid and H2. The catalyst enables selective acetic acid production of beverage bottles without pretreatment, providing a sustainable route for simultaneous waste plastic valorization and H2 production.

Photocatalytic selective upcycling of polyethylene terephthalate (PET) waste into valuable C2 products is an ideal strategy. However, over-oxidation and nonselective activation of C─C/C─O bonds by active sites in the local microenvironment have limited prior studies to produce C2 products. By designing Pt/ZnO-ZIS catalysts that feature a dynamically coupled Pt-In dual-site synergistic interface, this study achieves in situ upcycling of PET wastes via tuning the electronic structure and chemical environment of the Pt-In active sites and optimizing the adsorption configuration of plastic wastes. The dual active sites (Pt-In), which are spatially adjacent yet functionally distinct, achieves an HOAc production rate of 882.46 µmol g−1 h−1 with nearly 100% selectivity. Detailed characterizations and DFT calculations reveal that the high selectivity is attributed to the Pt sites adsorbing and protecting the terminal hydroxyl group (-OH) oxidation, and then activating the C─O bond to undergo proton substitution. The electron-rich Pt sites further inhibit the over-oxidation of C─C bond, ensuring high selectivity of HOAc. Simultaneously, the In sites facilitate oxidation of -OH to form carboxyl species during the reaction. This study provides an insightful understanding of dual sites with dynamic reconstruction toward highly selective photo-reforming of plastic wastes at the atomic scale.

The nature of ‘improper’ hydrogen bonds is explored in FnC─H⋯X systems, such as RCF2H interaction with chloride and water. It is noted that increased fluorination decreases the positive charge density on H but increases it on C, thus these interactions are dominated by electrostatic attraction to C over H. Such interactions map experimental blue and red shift IR phenomenon.

The RCH2F and RCHF2 groups are substituents of interest in medicinal and agrochemicals products. They have a polar aspect relative to the methyl (RCH3) or trifluoromethyl (RCF3) groups which results in a lowering of Log P's (water affinity). Here we use a computational approach to explore the nature of the interaction between RCH2F and RCHF2 in methanes and ethanes with chloride ion (and water), as a hydrogen bonding acceptor. A key observation is that the hydrogen atoms geminal to the fluorine(s) become less positively charged with increasing fluorination, a trend anticipated to weaken, not strengthen, their hydrogen bonding interactions. However this study demonstrates a dominating role for the electrostatic interaction of the acceptor with the CF carbons and profiles a shift in negative charge density from hydrogen to the carbon and fluorine(s) as chloride ion (or water) approach. The common occurrence of blue shifts (shortening C─H length) in these ‘improper’ or ‘non-classical’ hydrogen bonds is also explored and is correlated with the electrostatic interactions between the acceptor and the carbon atoms. These observations are extended to C3─C6 alicyclic rings containing these motifs and predict particularly strong interactions energies between chloride ion and specifically designed organo-fluoro alicycles.

A chiral narrow-band fluorophore undergoes aging-induced enhancement of fluorescence and circularly polarized luminescence (CPL) signals in the aggregate state, accompanied by a light-triggered aggregation-induced emission (AIE) to aggregation-caused quenching (ACQ) transition. The fusion strategy provides a straightforward and facile approach for constructing CPL materials with robust chiroptical performance.

The development of circularly polarized luminescence (CPL) materials has garnered considerable interest owing to their promising applications in areas such as 3D displays and information encryption, with most efforts devoted to generating CPL activity and improving the dissymmetry factor (g lum). However, the essential requirement of narrow-band emission for high-resolution organic optoelectronic applications is often overlooked. Here we employed the anthracene group as strong assembly unit and BODIPY as narrow-band fluorophore to construct with chiral binaphthyl moiety. The resulting compounds R/S-An-BDP displayed light-triggered transformation from aggregation-induced emission (AIE) to aggregation-caused quenching (ACQ) with CPL signals regulation. Moreover, R/S-An-BDP showed aging-driven narrow-band fluorescence with the full width at half maximum (FWHM) of 14 nm and CPL activity with the |g lum| value of 0.048 in the aggregate state, attributed to the combined effect of BODIPY and anthracene unit. These findings highlight a functional group fusion strategy for constructing CPL materials with large g lum values and narrow emission, offering a promising approach towards high-performance CPL materials.

Exploring the relationship between spin-state modulation strategy of low-Pt-based catalyst and pH-dependent oxygen reduction reaction (ORR) pathways can effectively alleviate oxygen-containing intermediates site-blocking effect, enhance ORR activity in acidic/alkaline conditions and further promote ORR kinetics in practical energy-storage/conversion devices.

The development of high-performance oxygen reduction reaction (ORR) electrocatalysts operable across broad pH ranges is hindered by strong adsorption of hydroxyl intermediates (*OH). This work introduces a conceptually novel strategy of spin-state modulation via interfacial engineering to regulate platinum nanocrystals anchored on atomically dispersed Fe-N-C substrates (Pt/FeSA-NC). Based on density functional theory (DFT) predictions, we construct a spin-state-tunable architecture by precisely controlling Pt particle size (2–8 nm), which induces spin-matching effects that effectively mitigate *OH over-binding in pH-dependent ORR path. Mechanistic studies indicate that the synergy between FeN4-mediated metal-support interactions and size-dependent spin polarization facilitates charge transfer, weakening *OH adsorption and promoting its desorption. In alkaline conditions, ∼2 nm Pt nanoclusters with moderate spin density achieve a peak power density of 179 mW cm−2 in Zn-air batteries with 150 h stability. Under acidic media, ∼8 nm Pt nanoparticles with low-spin configuration deliver a mass activity of 0.65 A mgPt −1 and a peak power density of 730 mW cm−2 in proton-exchange membrane fuel cells (PEMFCs), outperforming commercial Pt/C and retaining 90% activity after 3000 cycles. This finding provides a spin-engineering paradigm for designing advanced electrocatalysts with ultralow Pt loading.

A composite polymer electrolyte featuring dual-domain-coupled secondary nanoconfinement is constructed via precise polymer–nanodomain engineering. The mesoporous framework and dynamic polymer segments form interconnected ion pathways. In addition, anchoring domains with high negative surface potentials preload Li+, enhancing ion density and conductivity.

High-voltage solid-state lithium metal batteries (HVSSLMBs) integrate high-voltage cathodes (HVCs) with lithium metal anodes, offering great promise for next-generation energy storage. However, high-voltage charging induces lattice oxygen oxidation at the cathode, generating reactive oxygen species (ROS) that degrade inorganic solid electrolytes. In addition, the low room-temperature ionic conductivity and limited electrochemical stability of polymer electrolytes hinder their application with HVCs. Here, we design a composite polymer electrolyte (CPE) with dual-domain-coupled secondary nanoconfinement via precise polymer–nanodomain engineering. This structure combines a mesoporous framework with dynamic segmental motion, forming interconnected ion channels between free and anchored domains. The anchoring domains with high negative surface potential preload lithium ions, thereby increasing the local ion density and promoting a continuous high-conductance path. Benefiting from the protection mechanism of the nanoconfined system, the chemical stability of the polymer is greatly improved, thus achieving operation at high voltage. Cells paired with 4.8 V LRMO (Li1.2Ni0.13Co0.13Mn0.54O2) retained 80.37% capacity after 200 cycles. Notably, this study reported the first-ever assembly of a large-format pouch cell combining a CPE with the LRMO cathode, delivering an impressive energy density of 419.47 Wh kg−1 at a capacity of 4.61 Ah. This advancement marks a significant milestone in the application of HVSSLMBs.

“The most important thing I have learned from my students is to never stop asking “naïve” questions. Their fresh perspectives, unburdened by established dogma, often challenge my assumptions and lead to the most innovative approaches… I get my best ideas when I'm not actively trying to have them. They often appear during a long walk, in the shower, or right as I'm waking up…”

Find out more about Xiao-Hui Yang in her Introducing… Profile.

This work investigates the self-organization mechanism in nucleobase/peptide dynamic reaction networks, where environmentally responsive assemblies regulate network equilibria through cooperative/competitive replication behaviors, further achieving signal transduction across molecular networks through base-pairing.

The development of complex, adaptive behaviors in chemical systems hinges on the intricate coupling between reaction networks and self-organizing processes. Self-assembling networks, particularly those capable of self-replication, provide a unique platform for studying how molecular interactions drive temporally evolving, system-level behaviors. While environmental factors are known to shape the dynamic evolution of such networks, most studies have focused on static or single-class systems, such as isolated peptides or nucleic acids. This approach overlooks two critical dimensions of complexity: 1) nonlinear interspecies dynamics in multicomponent systems, and 2) inter-network coupling phenomena. Here, we investigate dynamic nucleopeptide networks exhibiting environment-responsive self-assembly, demonstrating how nucleobases and short peptides dynamically synergize under specific conditions to form organized, self-replicating structures. And we reveal how such networks orchestrate the interplay between cooperative and competitive species to achieve dynamic adaptation to environmental parameters (e.g., pH, temperature, and ionic strength). Furthermore, inspired by nucleobases’ genetic information function, we utilized the base-specific recognition in nucleopeptide assemblies for hierarchical network coupling—transmitting environmental signals from stimulus-sensitive to stimulus-insensitive systems. These findings offer new insights into temporal and cross-network regulation of self-assembly and reaction dynamics, providing a framework for designing adaptive, life-like chemical systems that evolve and communicate with environmental signals.

Electrooxidation enables tunable halocyclization of ambident amides, yielding either C–O or C–N products through ionic or radical pathways, respectively. While detailed experimental and analytical mechanistic studies highlight mode-dependent selectivity, in silico experimentation provided insight into the energetic origin of this divergence.

Herein, we report a divergent electrochemical halocyclization of ambident amides that enables selective formation of either C–O or C–N bonds. Unique chemoselectivity is governed by anodic oxidation conditions, in which haliranium-mediated C–O bond formation proceeds via chloride oxidation, while amidyl radicals guide C–N bond formation under basic conditions. Various approaches to understanding reaction mechanisms have been performed, including cyclic voltammetric analyses, experimental kinetic studies, and in silico experimentation. The developed electrooxidative synthetic method offers broad functional group tolerance, highlighting electrochemistry as a powerful tool for selective halocyclization.

The polarized N⁺ center establishes a charge-transfer (C-T) state, which promotes surface oxidation to steer the 2e− water oxidation pathway, suppresses H2O2 decomposition, and stabilizes the *OOH intermediate through electrostatic interactions, inhibiting further O─O bond cleavage.

Achieving selective two-electron water oxidation (2e− WOR) for sustainable hydrogen peroxide (H2O2) synthesis, while suppressing the competing four-electron oxygen evolution (4e− OER), represents a formidable challenge in artificial photosynthesis. The difficulty lies in the inherent vulnerability of the *OOH intermediate to over-oxidation or disproportionation, which triggers uncontrollable chain side reactions and naturally biases the reaction toward the less selective 4e− OER pathway. Here, we present a surface-engineering strategy utilizing a ZnCdS2 photocatalyst functionalized with polarized N⁺ surfactants, enabling molecular-level control over interfacial water oxidation pathways by establishing a charge-transfer (C-T) excited state. The polarized N⁺ centers effectively reconfigure the surface electronic states through molecular-scale polarization, achieving i) precise modulation of hole potentials and ii) stabilization of the *OOH intermediate, thereby promoting a direct 2e− WOR pathway. Without the use of any sacrificial reagents, this design achieves an exceptional H2O2 production rate of 2.37 mmol·g− 1·h− 1 (20.26 times of pristine ZnCdS2) statically and the scalable outlet concentration of 1.61 mM through a serial micro-batch flow reactor. By bridging atomic-level charge control with macroscopic catalytic performance, our work offers a proof-of-concept advance in C-T excited state driven photocatalysis, highlighting how surface electronic states can drive selective multi-electron reactions.

Cationic covalent-organic-framework as a bifunctional host enables efficient proton transport and enhanced battery cyclability performance, outperforming the previously reported solid-state proton battery (PB) systems.

Despite promising prospects afforded by high power density and abundant proton sources, proton batteries (PBs) face practical limitations. Liquid electrolytes induce anode dissolution and parasitic reactions, while solid electrolytes suffer from low proton conductivity and poor electrode compatibility. Herein, we introduce a bifunctional strategy for PBs using a cationic covalent organic framework (EB-COF). Synthesized from ethidium bromide (EB) and 2,4,6-triformylphloroglucinol (TP), this bifunctional host simultaneously stabilizes phosphomolybdate (PMo12) clusters anode and confines H3PO4 as a solid-state electrolyte within its nanochannels. The resulting EB-COF:H3PO4 electrolyte exhibits superior proton conductivity (>10−2 S cm−1) and a wide electrochemical stability window (3.3 V versus SCE). The assembled PB delivers exceptional rate capability and cycling stability, retaining 91% capacity over 15 000 cycles at 10 A g−1, surpassing all reported solid-state PBs. This performance stems from excellent electrode-electrolyte compatibility and the high structural stability of the EB-COF:H3PO4 system. This study provides valuable insights for developing reliable all-solid-state PBs.

We report the first enantioselective Rh-catalyzed reductive hydroformylation of alkenyl boronic esters. By employing either a “camouflage” or “direct” reductive asymmetric hydroformylation strategy, the enantiodivergent synthesis of chiral γ-boryl alcohols proceeds in high yields and excellent enantioselectivities with alkene 1,2-diboronic esters or alkenyl boronic esters as the starting materials and using rhodium/Ph-BPE as the catalyst.

We herein report the first enantioselective Rh-catalyzed reductive hydroformylation of alkenyl boronic esters. By employing either “camouflage” or “direct” reductive AHF strategy, enantiodivergent synthesis of chiral γ-boryl alcohols has been developed for the first time in high yields and excellent enantioselectivities with alkene 1,2-diboronic esters or alkenyl boronic esters as the starting materials using rhodium/Ph-BPE as the catalyst. The method has enjoyed high chemo-selectivity, good functional group compatibility, and broad substrate scope. The chiral γ-boryl alcohol or diol products are versatile building blocks applicable to the synthesis of a series of APIs including (S)-tolterodine, (S)-dapoxetine, and (R)-atomaxetine. DFT calculation has revealed the origin of enantiodivergence of Rh-catalyzed reductive AHF of alkenyl boronic esters with Ph-BPE as the chiral ligand. The transformation is promised to provide great synthetic potential in both academia and industry.

We report herein three emissive allyl radicals via conjugated extension of benzo[b]thiophene 1,1-dioxide and 1,3,5-trichlorobenzene protection. p-Tolyl and triphenylamine substitutions successfully produce stable allyl monoradicals, ARS-Ph and ARS-TPA, respectively. Whereas chlorine substituent affords an unexpected heterocoupled diradicaloid ARS-HD. Notably, ARS-TPA exhibits NIR fluorescent emission at 860 nm.

Air-stable luminescent monoradical remains rare. Herein, we report novel stable allyl radicals (ARS) achieved by conjugated extension of benzo[b]thiophene 1,1-dioxide and steric protection of 1,3,5-trichlorobenzene. The reactivity and photophysical properties of these allyl radicals are strongly dependent on protecting groups. Introducing p-tolyl group or triphenylamine afforded air-stable monoradical ARS-Ph and ARS-TPA, respectively. ARS-Ph displays doublet luminescence at 752 nm with negligible photoluminescent quantum yield (PLQY). ARS-TPA exhibits NIR fluorescence at 860 nm with a PLQY of 11.7%. Whereas, chlorine-protected ARS-Cl proved inaccessible, an unsymmetric heterocoupled dimer ARS-HD was isolated as a luminescent singlet diradicaloid with emission at 790 nm and a PLQY of 0.8%. Natural transition orbital analysis reveals the local excitation nature of ARS-Ph, excited charge-transfer characteristics of ARS-TPA and ARS-HD. Huang-Rhys factor and reorganization energy analyses of ARS-TPA disclose the critical effects of the vibrational decoupling and structure rigidity for its enhanced emission intensity and spectral sharpness. Remarkably, under continuous 365 nm light, ARS-Ph, ARS-TPA, and ARS-HD exhibit excellent luminescent photostability in ambient conditions with half-lives of 19.7, 42.6, and 21.4 h, respectively. Our study presents a straightforward strategy for developing air-stable luminescent allyl radicals, expanding the family of luminescent radical materials.

The chemo- and regiodivergent allyl-propargyl cross-coupling reactions of propargyl carbonates with allyl boronates has been realized. The role of ligands in determining both the chemoselectivity and regioselectivity is of particular importance, as they modulate the 1,1′- or 3,3′-reductive elimination mode from the same η3-allyl-η1-allenylpalladium intermediate.

Catalyst-controlled divergent transformations represent a vital strategy for the efficient production of structurally diverse molecules from the same readily available precursors. Herein, we report the palladium/phosphine-catalyst-driven chemo- and regiodivergent allyl-propargyl cross-coupling of propargyl carbonates with allyl boronates. Density functional theory (DFT) calculations reveal that the bidentate phosphine ligand plays a crucial role in determining the relative favorability of possible reductive elimination modes from the ƞ3-allyl-ƞ1-allenyl palladium intermediate species. Specifically, MeO-BIPHEP facilitates the 1,1′-reductive elimination to form the 1,4-enallenes; in contrast, XantPhos favors the formation of 1,5-enynes through a 3,3′-reductive elimination pathway.