Radical coupling of alkenes provides a powerful platform for constructing multiple bonds in a single operation, enabling the rapid generation of molecular complexity. However, controlling chemo- and regioselectivity remains a key challenge in this approach, especially when multicomponent radical intermediates are involved. Herein, a visible-light induced regioselective alkyl-acylation of alkenes has been developed by using carboxylic acids and their derivatives (NHPI ester) as the coupling partners. This synergistic combination of decarboxylation of NHPI esters and phosphoranyl radical-mediated deoxygenation protocol requires no external oxidants or reductants, and facilitating the generation of alkyl radical and acyl radical under mild and redox-neutral conditions. A wide range of highly functionalized ketone products have been constructed in good yields with high regioselectivity from readily available carboxylic acids and alkenes. The mechanistic studies support a radical cascade pathway involving two photogenerated radicals and alkenes, and DFT calculations demonstrate that the high regioselectivity arises from kinetically controlled radical addition and radical/radical cross-coupling process. In addition, this strategy can be explored to realize regioselective radical dialkylation of alkenes, producing molecules with sterically congested all-carbon quaternary centers in moderate yields. This robust strategy exhibits excellent functional group tolerance, gram-scale ability, and has been applied in the late-stage functionalization of bioactive natural compounds, thereby providing a new approach to functionalized ketones from carboxylic acids and derivatives.

Ni-rich LiNi_xCo_yMn_zO₂ (NCM) materials are regarded as one of the most promising candidates for next-generation lithium-ion batteries due to their high specific capacity. However, their mechanical degradation during cycling leads to significant capacity fading. Electrochemical–mechanical coupled modeling is an effective strategy for understanding the underlying mechanisms of mechanical degradation. Nevertheless, studies involving the simulation and experimental validation of macroscopic electrode stress remain insufficient. This work delineates the multi-scale lithiation-induced strain process in NCM materials and establishes a three-dimensional heterogeneous electrochemical-mechanical coupled model that successfully predicts the macroscopic stress evolution in NCM811 electrodes. Sufficient physical justification and experimental validation are provided for the isotropic simplification of anisotropic single-crystal particles. The simulations reveal the rate performance of particles across different sizes, identifying potential locations of mechanical failure. These findings underscore the importance of macroscopic stress signals in reflecting the electrochemical state of electrodes and provide a validated tool for analyzing battery behavior based on stress information.

Catalytic activity and durability represent a long-lasting dilemma in catalytic applications of metal nanoparticles. Herein, we report a dehydration-rehydration strategy for immobilizing metal nanoclusters (NCs, <3 nm nanoparticles) on MgAl layered double hydroxides (MgAl-LDHs) for simultaneously promoting their catalytic activity and durability. This approach relies on the reversible dehydration-rehydration process of MgAl-LDHs, in which anionic Au₂₅(p-MBA)₁₈ NCs (p-MBA = para-mercaptobenzoic acid) can be effectively tethered on positively charged MgAl hydroxide layers to yield Au₂₅/LDH composites. The strong electrostatic interactions of 2D MgAl hydroxide layers with carboxylate groups of p-MBA ligands are effective in re-orientating the p-MBA ligands on cluster surface, exposing more active Au sites for catalytic reactions. Such enhanced active Au site accessibility is conducive to improving catalytic activity of Au₂₅/LDH composites toward selective reduction of 4-nitrophenol to 4-aminophenol. Au₂₅/LDH composites achieve complete conversion of 4-nitrophenol within 180 s with a rate constant of 0.0183 s^–1, while their catalytic activity remains uncompromised within ten catalytic cycles. This study not only provides a simple yet effective strategy for stabilizing and activating metal NCs for catalytic applications, but also affords an alternative mechanism for engineering the catalytic activity of metal NCs via ligand re-orientation.

Aiming at the polarization loss bottleneck in electromagnetic wave (EMW) absorbing materials, we propose a new bimetallic hybrid strategy towards multiphase solid solutions to increase multiple polarization losses. Assisted by polydopamine (PDA) as crystalline phase inducer, Mo/W substances were anchored in situ on carbon networks. As a result, a carbon-supported MoC_1–x/WC/W₂C/WC_1–x heterostructure was formed. This process leads to Mo migration and W occupying vacancies, resulting in vacancy/substitution defects. Simultaneously, Li⁺ is inserted into the solid solution to form an interstitial structure. Due to the synergistic effect of multiple polarization losses, the Mo2W-900 solid solution achieved excellent EMW absorption performance. The minimum reflection loss (RL_min) at a thickness of 2.5 mm is –65.92 dB, and it has a maximum effective absorption bandwidth (EAB_max) of 6.16 GHz at only 2.1 mm. This paper establishes a new type of multi-loss polarization model for solid-solution absorbers, providing important theoretical guidance for the design of the next generation of hybrid absorbers.

C–B axially chiral compounds constitute a significant class of stereogenic molecules with growing importance in advanced materials science and pharmaceutical chemistry, particularly as chiral ligands, functional building blocks, and bioactive scaffolds. However, the catalytic asymmetric construction of such stereogenic axes remains a formidable synthetic challenge, primarily due to the elongated C(sp²)-B bond length and its correspondingly low rotational energy barrier, which often leads to configurational instability. To date, asymmetric catalytic synthesis of C – B axially chiral compounds has predominantly employed metal catalysis, whereas organic catalytic strategies remain scarce. In this work, we disclose a highly efficient organocatalytic kinetic resolution (KR) strategy for the selective synthesis of enantioenriched C–B axially chiral compounds. Our method employs a readily accessible tetraimidazole catalyst and utilizes isobutyric anhydride as reactive substrates. This protocol affords the desired axially chiral boranes in high yields and excellent enantioselectivities (with selectivity factor up to 121). The practical utility of this methodology was demonstrated through successful gram-scale synthesis and a series of downstream functional group transformations, highlighting its potential for synthetic applications. The racemization experiments established that the rotational barriers of the axially chiral compound was 41.7 kcal/mol, a value that confirms sufficient thermodynamic stability for the isolation, characterization, and further application of these compounds at ambient conditions. Mechanistic investigations, including a set of control experiments, revealed a critical dual role of the iodine atom present in the reaction: it not only provides steric bulk to impede the rotation around the C–B bond but also plays an important role in governing the stereochemical outcome of the reaction. In addition, the origin of enantioselectivity was elucidated through density functional theory (DFT) calculations.

Photo-enhanced zinc-air batteries (PZABs) offer a promising approach to coupling solar energy with electrochemical energy conversion, yet their performance remains limited by rapid charge-carrier recombination and insufficient light-harvesting efficiency. Here, we propose a dual-vacancy engineering strategy for NiCrO-based oxides to simultaneously introduce oxygen and chromium vacancies (NCOV-Cr, O). The synergistic effect of these vacancies effectively suppresses carrier recombination, enhances photogenerated electron capture, and promotes the in-situ formation of highly active nickel oxyhydroxide (NiOOH) phases. This structural modulation strengthens the adsorption and activation of *OH intermediates by 1.5 times, providing a stronger thermodynamic driving force for redox processes. As a result, the NCOV-Cr, O photocathode achieves excellent multifunctional catalytic activity with an onset potential of 0.95 V for the ORR, and low overpotentials of 255 and 33 mV for the OER and HER, respectively. When integrated into a PZAB, the device delivers an ultralong cycling life exceeding 450 h and a peak power density of 253.9 mW·cm⁻² under one-sun illumination. This work showcases that tailoring vacancy defects which recombine the ligand coordination environment creates novel avenues for boosting catalytic performance.

Spiroketals have gathered considerable attention owing to their prevalence in ligands, pharmaceuticals, and natural products. Their three-dimensional complexity often imparts desirable biological activity. Nevertheless, enantioselective synthesis of spiroketals still represents considerable challenges. Herein, we report a Pd/PC-Phos-catalyzed enantioselective nucleophilic dearomatization of furfural N-sulfonylhydrazones with readily available aryl halides. Up to 96.5 : 3.5 er, 99/1 Z/E and 73% yield have been achieved. Moreover, the reaction exhibits broad substrate compatibility, good functional group tolerance, easy scalability and versatile product functionalization. This protocol enables the synthesis of chiral spiroketals in high enantioselectivity and Z/E selectivity that have limited previous synthetic access. In addition, the origins of enantioselectivity were further rationalized using density functional theory calculations. The enantio-determining step is speculated to be the carbenation process.

Cyclopropane is a unique ring motif widely incorporated into pharmaceuticals to enhance their potency. Developing synthetic methods for the efficient construction of cyclopropanes, particularly those with functional groups, is of both practical significance and academic interest. Among the reported methods, the reduction of gem-dihalides followed by cyclization with alkenes represents one of the most efficient and straightforward [2+1] approaches. However, most references rely on photochemical pathways, which severely limit practical applications. Additionally, electrochemical catalytic reduction of halides has gained significant attention in recent years, primarily using nickel and cobalt catalysts. In this study, we introduce an iron-mediated electrochemical reduction of borodiiodomethane, followed by cyclopropanation with alkenes, enabling rapid fabrication of cyclopropylboronates. Substrates with a wide range of functional groups are well tolerated, demonstrating the ease of late-stage modifications. Gram-scale synthesis, conducted without extending reaction time and maintaining the same current density, yielded similar results, highlighting the method's practical application. The boronate group on the cyclopropane can be easily transformed, paving the way for further applications in medicinal chemistry. Notably, mechanistic investigations, including control experiments and cyclic voltammetry studies, revealed that iron species—both the Fe salt and the Fe/2,2'-biquinoline complex—can effectively promote electrochemical cyclopropanation. Given that iron is an inexpensive material, its dual role as both sacrificial anode and promoter enhances the practicality of this method.

Due to the high activation barriers associated with cleaving both C–H bonds and the N≡N triple bond, achieving C–N bond formation from relatively inert C–H bonds as carbon sources under mild conditions has long posed a major challenge in synthetic chemistry. To address this long-standing issue, we have developed a novel and straightforward approach for the synthesis of carbazoles, using N₂ as the nitrogen source and 2-bromobiaryls as the carbon partner through an engineered one-pot/two-step protocol. The key to this protocol lies in the in-situ generation of lithium nitride (Li₃N) from N₂ using lithium as the reductant, which serves as a primary intermediate. This intermediate then undergoes a Pd-catalyzed process involving successive C(sp²)–Br bond activation and intramolecular C(sp²)–H bond functionalization to form the target carbazole framework. Notably, this strategy exhibits a broad substrate scope, excellent tolerance towards various functional groups, and high regioselectivity. Leveraging this method, we have successfully synthesized a diverse range of high-value carbazoles directly from N₂, including biologically active natural alkaloids (such as the anti-HIV drug Glycoborine and the antiviral compound Clausine V), optoelectronic materials (e.g., 11,12-dihydroindolo[2,3-a]carbazole), and ¹⁵N-labeled carbazoles. This approach not only expands the scope of carbon sources suitable for nitrogen incorporation from N₂ but also paves potential pathways for the development of diverse catalytic systems, offering new opportunities for the efficient synthesis of nitrogen-containing heterocycles.

A highly efficient catalytic enantioselective [4+2] annulation reaction between acyclic or cyclic enecarbamates and in situ-generated azoalkenes (derived from α-halohydrazones) has been successfully realized using a Cu(I)/(4R,2R_p)-Ph-Phosferrox complex. Performed under mild reaction conditions, this robust synthetic protocol affords a structurally diverse collection of chiral tetrahydropyridazine derivatives bearing multiple contiguous stereogenic centers, with good to excellent isolated yields (48%–94%), high enantioselectivities up to 96% ee, and excellent diastereocontrol (dr > 20 : 1). This reaction also exhibits outstanding substrate generality and tolerance, accommodating a wide scope of substituted α-halohydrazones and structurally varied enecarbamates, thereby enabling the facile construction of a diverse library of functionalized chiral tetrahydropyridazines. A gram-scale experiment and subsequent synthetic derivatizations of the chiral products were conducted to fully verify the practical utility and scalability of this catalytic system for potential synthetic applications. Single-crystal X-ray diffraction analysis of a representative product unambiguously confirmed its absolute configuration, and combined with systematic control experiments, these results clarified that the annulation proceeds through a stepwise [4+2] cycloaddition pathway. Additionally, comprehensive mechanistic studies including nonlinear effect assays, UV absorption spectroscopic analyses and Job's plot measurements were performed, which together provide solid experimental evidence to firmly validate the scientific rationality of the proposed reaction mechanism.

This study establishes a highly enantioselective nickel-catalyzed reductive cross-coupling strategy that directly converts ubiquitous malonic acid derivatives into valuable chiral α-aryl and α-alkenyl esters. The protocol employs stable redox-active esters (RAEs) as practical alkyl radical precursors, which undergo decarboxylative coupling with a wide array of (hetero)aryl and alkenyl halides under mild reductive conditions. A central achievement is the identification of a tailored chiral bis-imidazoline (BiIM) ligand, which is critical for achieving exceptional stereocontrol over the prochiral, electrophilic radical intermediate generated in situ—a longstanding challenge in asymmetric synthesis. The reaction demonstrates remarkable generality with respect to both coupling partners. A broad spectrum of malonic acid-derived RAEs bearing diverse α-substituents, including linear and branched primary alkyl groups, benzyl groups, heterocycles, and sterically hindered secondary alkyl groups, are all compatible substrates. The electrophile scope is equally comprehensive, successfully incorporating aryl bromides and iodides with either electron-withdrawing or electron-donating substituents, various pharmaceutically relevant heteroaryl halides, and alkenyl bromides. Products are consistently obtained in good yields and with excellent enantioselectivity. The synthetic utility of this method is underscored by its operational simplicity, excellent functional group tolerance, and successful application in the late-stage functionalization of complex drug-like molecules, enabling the efficient synthesis of enantioenriched hybrids. Mechanistic investigations, including radical trapping and clock experiments, support a reaction pathway involving a key alkyl radical intermediate. Collectively, this work provides a powerful, modular, and practical platform for the direct construction of enantioenriched C(sp³)–C(sp²) linkages from simple and inexpensive feedstocks, with significant potential for accelerating discovery in medicinal chemistry and asymmetric synthesis.

The ipso, para-C–H difunctionalization of substituted arenes remains a persistent challenge in synthetic chemistry. In this work, we address this problem by strategically introducing two new elementary steps—radical para-amination and deprotonation—into the well-established radical-polar crossover aryl migration framework. This maneuver elegantly diverts the reaction pathway from a simple aryl migration to a novel ipso/para-difunctionalization, illustrating how classic mechanistic paradigms can be “evolved” to address unmet synthetic needs. Employing oxime esters as bifunctional radical precursors under energy transfer (EnT) photocatalysis, the reaction enables ipso N–C interconversion coupled with para-amination of anilines bearing a tethered remote alkene. Mechanistically, the process involves EnT-promoted N–O bond homolysis, trapping of the alkyl radical by SO₂, sulfonyl radical addition to the alkene, intramolecular ipso-cyclization, radical–radical cross-coupling between a transient cyclohexadienyl radical and a persistent iminyl radical, and finally a deprotonation-driven aryl migration. The protocol demonstrates remarkable generality, accommodating a broad range of ortho- and meta-substituted aniline derivatives with diverse electronic and steric properties. This wide substrate tolerance, along with the observed specific ipso, para-selectivity, is governed primarily by the intrinsic nature of the transformation rather than conventional electronic or steric parameters. Mechanistic studies, including control experiments, radical-trapping assays, and quenching experiments, support the proposed EnT pathway and the radical-polar crossover cascade. DABSO plays a dual role: it serves as an SO₂ source to convert nucleophilic alkyl radicals into electrophilic sulfonyl radicals, while also releasing DABCO as a base to facilitate the final deprotonation step. This method provides efficient and modular access to valuable 4-aminated benzenepropanamide scaffolds, and offers a new disconnection strategy for remote C–H functionalization that synergistically merges radical and ionic processes. More broadly, this work highlights how strategically incorporating additional elementary steps into established mechanisms can significantly expand the synthetic toolbox.

Lithium-ion batteries subjected to extreme operating conditions—such as high temperature, high C-rates, and deep overdischarge— exhibit rapid and coupled aging behaviors that are challenging to disentangle using conventional diagnostics. While purely data-driven models often lack interpretability ("black-box"), physics-based methods typically require measurements unavailable in practical applications. To bridge this gap, we propose the SIX-ICA framework, an interpretable machine learning approach that integrates Incremental Capacity Analysis (ICA) features with an XGBoost regressor and SHAP analysis. By extracting mechanism-informed ICA peak features from routine cycling data, the framework achieves robust State-of-Health (SOH) estimation. Crucially, SHAP analysis provides transparent feature attribution, linking statistical inputs directly to degradation pathways. Validated on LiFePO₄/graphite pouch cells cycled at 65 °C and 3 C (comparing 2.5 V vs. 1.0 V cutoffs), the framework identifies Loss of Lithium Inventory (LLI) as the primary driver of capacity fade, noting its significant intensification under deep over-discharge, while Loss of Active Material (LAM) plays a secondary role. These findings are corroborated by OCV fitting and post-mortem characterization. This workflow advances interpretable SOH diagnostics under extreme conditions and offers a scalable route for other battery chemistries.

The development of efficient and sustainable methods for carbonyl addition reactions remains a central focus in organic synthesis. The Nozaki–Hiyama–Kishi (NHK) reaction provides a compelling alternative to classical nucleophilic carbonyl additions with preformed organometallic reagents, and significant advancements have been made over the past decades. However, its application to unactivated halides has long been hindered by their prohibitively negative reduction potentials, which are resistant to single-electron transfer (SET) reduction. Herein, we circumvent this challenge by utilizing a halogen-atom transfer (XAT) strategy, and report a photoredox/Cr dual catalytic system for the carbonyl addition of unactivated alkyl bromides. The key to the success of this reaction is the judicious choice of silanol as the XAT reagent, which enables the transformation of unactivated alkyl bromides into the corresponding alkyl radicals through a silyl radical-mediated XAT process. This protocol operates under mild conditions and exhibits an exceptionally broad substrate scope, and good functional group compatibility, accommodating a wide range of unactivated primary, secondary, and even tertiary alkyl bromides, as well as various alkyl and aryl aldehydes, providing a robust platform for the synthesis of alcohols. Moreover, this method effectively enables the late-stage functionalization of complex molecules derived from natural products and pharmaceuticals, underscoring its practical utility. Preliminary mechanistic investigations suggest a pathway in which alkyl radicals are intercepted by a chromium species through a radical–polar crossover process to form nucleophilic alkyl–chromium(III) complexes that undergo addition to carbonyl compounds. This work further highlights the versatility and broad compatibility of chromium-based cooperative catalytic systems in carbonyl addition chemistry.

α-Trifluoromethyl amidines and imidates represent privileged molecular scaffolds due to the prevalence of amidine/imidate motifs in bioactive compounds and functional materials, coupled with the ability of the CF₃ group to enhance key physicochemical and pharmacological properties. Nevertheless, general methods for their synthesis remain underdeveloped. Herein, we report a mild, metal- free photocatalytic strategy that enables the modular assembly of these valuable structures with perfect atom economy. The protocol involves the in situ generation of 3-(trifluoromethyl)ketenimines from readily accessible trifluoroacylsilanes and isocyanides, followed by nucleophilic trapping with anilines and phenols. This operationally simple method exhibits a broad substrate scope, high efficiency, and generally delivers products in good yields. Mechanistic investigations, supported by density functional theory (DFT) calculations, indicate that the reaction proceeds preferentially via a triplet carbene intermediate, and a plausible mechanism for the pivotal coupling step is proposed.

Described here is an unusual palladium-catalyzed dihalogenative endo cyclization of unactivated 1,6-enynes. In sharp contrast to previous related studies, which have long been restricted to activated electron-deficient enynes and/or exclusively resulted in exo cyclization, the present process for the first time enables unactivated 1,6-enynes to overcome the inherent kinetic tendency toward 5-exo-trig cyclization and lead to the kinetically disfavored 6-endo-trig pathway. This distinctive cyclization mode is inconsistent with classical Baldwin's rules, which typically favor the formation of five-membered rings through exo-trig cyclization due to kinetic advantages and lower energy barriers. Both dibromination and dichlorination transformations are successfully achieved under optimized reaction conditions, employing a palladium catalyst in combination with a copper halide salt, an appropriate base and solvent system to ensure high reactivity, excellent regioselectivity, and outstanding stereoselectivity. This synthetic strategy facilitates the rapid and efficient construction of highly functionalized six-membered heterocycles, including piperidines and tetrahydropyrans, as well as carbocycles, all of which exhibit satisfactory overall performance across a broad substrate scope encompassing aryl, heteroaryl, and alkyl substituents on the enyne scaffold. The resulting products possess two versatile carbon-halogen bonds, including C(sp²)-X and C(sp³)-X type, and a stereodefined olefin with excellent >20 : 1 E/Z selectivity, rendering them valuable building blocks for subsequent organic transformations. Control experiments further confirm the essential roles of both palladium and copper salts in promoting the reaction, while preliminary DFT calculations shed light on the origin of reaction selectivity and the cyclization mechanism. Collectively, all these features underscore the significant synthetic utility of this newly developed cyclization protocol in modern organic synthesis.

Silicon-stereogenic silacarbocycles constitute a privileged class of organosilicon compounds with wide-ranging applications in asymmetric synthesis, functional materials, and medicinal chemistry. This review provides a systematic overview of recent advances in catalytic enantioselective synthetic methods, organized by catalytic systems, and traces the evolution of key strategies—with particular emphasis on desymmetrization of prochiral precursors, alongside kinetic resolution (KR) and dynamic kinetic asymmetric transformation (DYKAT). The field was initially established through pioneering Pd-catalyzed transformations, notably the asymmetric ring-expansion of strained silacyclobutanes with alkynes—a fundamental methodology for constructing cyclic tetraorganosilicon stereocenters. Subsequently, Rh-catalyzed systems have emerged as highly versatile platforms, enabling diverse transformations including dehydrogenative C–H silylation for accessing monohydrosilanes and heterocycles, intramolecular hydrosilylation toward cyclic monohydrosilanes and spirosilabiindanes, and formal [2+2+2] cycloadditions for synthesizing dibenzosiloles and silaspiranes. Driven by economic and sustainability considerations, research has fruitfully expanded to encompass earth-abundant base metal catalysis. Ni-catalyzed systems facilitate efficient intramolecular aryl transfer and ring-expansion reactions, while Co- and Cu-catalyzed approaches enable sequential hydrosilylation cascades that construct silacycles bearing consecutive Si and C stereocenters. Concurrently, metal-free organocatalysis has emerged as a powerful sustainable alternative, with chiral N-heterocyclic carbenes (NHCs), chiral phosphoric acids (CPAs), enamine catalysts, and confined imidodiphosphorimidates (IDPi) demonstrating remarkable efficacy in enantioselective desymmetrization processes. Despite substantial progress, we also offer a critical perspective on current methodologies, outline existing challenges and limitations, and highlight promising directions for future research. Current limitations include reliance on elaborate prochiral substrates and historical dependence on precious metals. Future efforts should focus on developing more efficient and atom-economical substrate synthesis, expanding sustainable catalytic systems including base-metal, organo-, and biocatalysis, integrating emerging technologies such as photocatalysis and electrocatalysis, and deepening mechanistic understanding to enable the rational design of advanced strategies such as DYKAT.

In 2011, Hayashi and Shintani reported a pioneering Pd-catalyzed asymmetric ring expansion of silacyclobutanes with alkynes, enabling the construction of cyclic tetraorganosilicon stereocenters and marking the inception of this field. Subsequently, Takai and coworkers developed a Rh-catalyzed asymmetric synthesis of chiral spirosilabifluorene through sequential Si–H and C–H bond activations. In 2015, Nozaki and Shintani developed an efficient Rh-catalyzed [2+2+2] cycloaddition for the highly enantioselective synthesis of Si-stereogenic dibenzosiloles. In 2018, Xu and colleagues established a Pt-catalyzed tandem hydrosilylation/cyclization, and in 2022, the same group made further breakthroughs in the Rh-catalyzed dynamic kinetic asymmetric hydrosilylation to access Si-stereogenic benzosiloles. Meanwhile, the Song group developed a Rh-catalyzed ring expansion of silacyclobutanes with alkynes, expanding the methodologies for synthesizing axially chiral spirosilanes. In 2021, He et al. made an important contribution through Rh-catalyzed C–H silylation, enabling the enantioselective synthesis of Si-stereogenic monohydrosilanes and various heterocycles. Concurrently, the group of Wang conducted impressive studies on Rh-catalyzed asymmetric hydrosilylation and established a kinetic resolution strategy for the efficient synthesis of Si-stereogenic cyclic monohydrosilanes. More recently, Zhao reported a base-metal-catalyzed intramolecular ring expansion and an Ir-catalyzed enantioselective C–H silylation for constructing Si-stereogenic silacarbocycles, thereby further broadening the catalyst scope in this area. Numerous other researchers have also made important contributions; however, due to space constraints, a comprehensive acknowledgment of all achievements is not feasible within this review.

Silicone rubber is widely used in fields such as automotive, aerospace, healthcare, and consumer goods due to its unique properties and robust structure. While many previous reviews focus on structure and intrinsic properties, this review highlights the connection between silicone rubber and real-world industrial applications. The material is generally classified into room temperature vulcanized (RTV), high temperature vulcanized (HTV), and liquid silicone rubber (LSR). Their curing mechanisms, typical formulations, and key performance parameters are systematically compared, along with their typical end-use areas such as sealants, electrical insulation, medical devices, and wearable components. Both conventional and emerging manufacturing methods are summarized. Recent advances, such as 3D printing, microfabrication, and roll-to-roll processing, are enabling cost-effective prototyping and reduced material waste compared to traditional molding techniques. Compared to traditional elastomers, silicone rubber exhibits superior thermal stability, chemical resistance, and processing flexibility, which supports its use in extreme environments. The development of modified systems and derivatives has further expanded functionality, providing flame retardancy, electrical conductivity, self-healing, and improved biocompatibility. New recyclable and stimuli-responsive types of silicone rubber also broaden opportunities in sustainable manufacturing, flexible electronics, and smart medical devices. Overall, this review links recent material modifications and advanced processing methods with expanding industrial applications, outlining both current achievements and key directions for future development in the silicone rubber field.

The N-heterocyclic carbene (NHC), as an electron-rich nucleophilic species, constitutes an important class of ligands for transition metals and plays a key role in organocatalysis. Consequently, diverse NHCs have been developed in recent years. Moreover, to access NHCs with novel scaffolds, innovative synthetic methods of NHC precursors have emerged. Given the prevalence of carbene precursors in organometallic and organocatalytic processes, this review summarizes the synthesis of imidazolium, imidazolinium, thiazolium, and triazolium salts. Finally, we propose future research directions for developing highly efficient novel NHCs.

Polyvinylidene fluoride (PVDF), the second largest produced fluoropolymer, exhibits outstanding chemical, physical, electroactive and electrochemical properties and is involved in many High-Tech applications. This review reports recent novelties in synthesis, characterization, processes and applications. Recent preparation studies deal with the effect of the additives (originally, fluorinated surfactants as PFOA, then hydrocarbon ones, whereas nowadays no surfactants are used), process (greener aqueous emulsion of suspension and abatements in process) to obtain high molar mass and crystallinity, better mechanical, ferro-, piezo- and triboelectric properties. The influence of the reaction temperature vs the Head-to-Head defects in PVDF chaining is highlighted. Recent studies on the reversible deactivation radical polymerization of VDF are also reported. Regarding per-and polyfluoroalkyl substance (PFAS) concerns, PVDF is not water soluble, not toxic, not bioaccumulative and does not cross the lipidic human membrane. Applications encompass electronics, healthcare, automotive, aerospace, energy (e.g., storage including lithium-metal technologies), industrial processing, driving the market growth. The current challenges are its recycling, reuse strategies or degradation without releasing PFAS to reduce environmental impact. Though PVDF market undergoes severe issues caused by PFAS restrictions, it has a CAGR of 7.2% driving the demand for efficient materials in increasing areas globally. Thus, PVDF continues being indispensable across many sectors.