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The design of heterogeneous catalysts generally involves optimizing the reactivity descriptor of adsorption energy, which is inevitably governed by the structure of surface-active sites. A prerequisite for understanding the structure–properties relationship is the precise identification of real surface-active site structures, rather than relying on conceived structures derived from bulk alloy properties. However, it remains a formidable challenge due to the dynamic nature of nanoalloys during catalytic reactions and the lack of accurate and efficient interatomic potentials for simulations. Herein, a generalizable deep-learning potential for the Ag–Pd–F system is developed based on a dataset encompassing the bulk, surface, nanocluster, amorphous, and point defected configurations with diverse compositions to achieve a comprehensive description of interatomic interactions, facilitating precise prediction of adsorption energy, surface energy, formation energy, and diffusion energy barrier and is utilized to investigate the structural evolutions of AgPd nanoalloys during fluorination. The structural evolutions involve the inward diffusion of F, the outward diffusion of Ag in Ag@Pd nanoalloys, the formation of surface AgFx species in mixed and Janus AgPd nanoalloys, and the shape deformation from cuboctahedron to sphere in Ag and Pd@Ag nanoalloys. Moreover, the effects of atomic diffusion and dislocation formation and migration on the reconstructing pathway of nanoalloys are highlighted. It is demonstrated that the stress relaxation upon F adsorption serves as the intrinsic driving factor governing the surface reconstruction of AgPd nanoalloys. [ABSTRACT FROM AUTHOR]

Ideal pathways to synthesize fluorinated compounds were pursued for over 100 years, due to wide application of organofluorides in materials, agrochemicals and pharmaceuticals. In this regard, electro‐organic synthesis, evolved as a sustainable and scalable approach in various synthetic protocols, stands out as a promising strategy. As a result, many novel and attracting applications of introduction of fluorine items into organic compounds by direct and redox‐mediated electrochemical methods has been reported, especially in recent five years. In this review, we are aim to highlight the reaction scopes, reaction mechanism, the fundamental aspects and the fluorine source variation in electrochemcial fluoriation transformation. [ABSTRACT FROM AUTHOR]

Direct fluorination has demonstrated efficacy in modulating the surface electrical properties of epoxy insulators and preventing surface charge accumulation. Comparative corona treatments were conducted on both surface fluorinated (modified) epoxy samples and untreated (virgin/original) samples using a modified electrode setup in a nitrogen (N2) atmosphere. The purpose was to evaluate the resistance of the modified epoxy surface layer against corona discharge. The results of ATR‐IR analysis and SEM surface and cross‐sectional imaging indicate that corona treatment did not alter the chemical composition of the fluorinated sample or the thickness of the fluorinated layer. Based on assessments of potential decay and water contact angle measurements, the surface conductivity of the modified sample was decreased by corona treatment. The wettability of fluorinated sample remained unchanged after corona treatment, and no soluble degradation products were produced. Conversely, the surface conductivity of the virgin sample exhibited an increase following corona treatment, accompanied by the formation of soluble degradation products. These results confirm that direct fluorination improves the epoxy insulator's discharge resistance in N2 and provides technical support for enhancing the electrical performance of epoxy insulators in gas insulated equipment. © 2024 Institute of Electrical Engineers of Japan and Wiley Periodicals LLC. [ABSTRACT FROM AUTHOR]

Sulfur based deoxyfluorination reagents are usually derived from the corrosive gas SF4. Herein, we report the synthesis and properties of an easily accessible phosphonium salt [(tmg)3PF]+SF5− (1) which was obtained from the reaction of sulfur hexafluoride (SF6) with tris(tetramethylguanidinyl)phosphine. The performance of this crystalline SF5− salt as a reagent in deoxyfluorination reactions was investigated together with a second SF5− salt [(R1)3PF]+SF5− (2) containing bulky substituents (R1=1,3‐di‐tert‐butylimidazolidin‐2‐ylidenamino). Both reagents proved to be effective for the deoxyfluorination of various functional groups including alcohols, anhydrides, and amides. [ABSTRACT FROM AUTHOR]

To enhance organic light emitting diode (OLED) performance, host materials with high triplet energies are crucial for confining excitons, despite increasing driving voltages due to the singlet‐triplet energy gap. We synthesized sulfonylbis(4,1‐phenylene)bis(3,6‐disubstituted‐9H‐carbazole) derivatives as donor‐acceptor‐donor host materials, namely compounds 3, 5 and 7, with varying fluorination levels. These compounds show moderate singlet‐triplet energy splitting and molecular dipole moments, allowing for fine‐tuning of hole‐transport mobilities, deeper frontier orbital energies, and a red shift in singlet emission while maintaining high triplet energy levels. These adjustments impact a range of physical, electronic and optical properties. The materials exhibit exceptional thermal stability, with decomposition starting above 400 °C and glass transition temperatures over 130 °C. Used with the green TADF emitter DACT‐II, these hosts enable reverse intersystem crossing rates between 7.43×104 s−1 and 1.77×105 s−1. While OLEDs using mCP as a reference host achieve a maximum quantum efficiency of 18.5 %, those with host 5 show lower efficiency roll‐off, leading to higher external quantum efficiency at brightness levels above 2000 cd/m2 without colour shift. The reduced roll‐off in devices with host 5 compared to mCP is attributed to effective Förster and Dexter energy transfers to DACT‐II at high currents, enhancing light emission pathways. [ABSTRACT FROM AUTHOR]

Efficient and environmentally benign regioselective halogenation protocols have been achieved through the mediation of oxone‐halide, with or without the assistance of aryl iodine. The key to the success of the regioselectivity process is the controlled generation of the active [X]+ or halogen‐substituted hypervalent iodine (III) by manipulating the components of the oxone‐halide‐aryl iodine system. [ABSTRACT FROM AUTHOR]

Gases are essential for various applications relevant to human health, including in medicine, biomedical imaging, and pharmaceutical synthesis. However, gases are significantly more challenging to safely handle than liquids and solids. Herein, we review the use of porous materials, such as metal‐organic frameworks (MOFs), zeolites, and silicas, to adsorb medicinally relevant gases and facilitate their handling as solids. Specific topics include the use of MOFs and zeolites to deliver H2S for therapeutic applications, 129Xe for magnetic resonance imaging, O2 for the treatment of cancer and hypoxia, and various gases for use in organic synthesis. This Perspective aims to bring together the organic, inorganic, medicinal, and materials chemistry communities to inspire the design of next‐generation porous materials for the storage and delivery of medicinally relevant gases. [ABSTRACT FROM AUTHOR]

The clinical translation of tumor hypoxia intervention modalities still falls short of expectation, restricted by poor biocompatibility of oxygen‐carrying materials, unsatisfactory oxygen loading performance, and abnormally high cellular oxygen consumption‐caused insufficient hypoxia relief. Herein, a carrier‐free oxygen nano‐tank based on modular fluorination prodrug design and co‐assembly nanotechnology is elaborately exploited, which is facilely fabricated through the molecular nanoassembly of a fluorinated prodrug (FSSP) of pyropheophorbide a (PPa) and an oxygen consumption inhibitor (atovaquone, ATO). The nano‐tank adeptly achieves sufficient oxygen enrichment while simultaneously suppressing oxygen consumption within tumors for complete tumor hypoxia alleviation. Significant, the fluorination module in FSSP not only confers favorable co‐assemblage of FSSP and ATO, but also empowers the nanoassembly to readily carry oxygen. As expected, it displays excellent oxygen carrying capacity, favorable pharmacokinetics, on‐demand laser‐triggerable ATO release, closed‐loop tumor hypoxia relief, and significant enhancement to PPa‐mediated PDT in vitro and in vivo. This study provides a novel nanotherapeutic paradigm for tumor hypoxia intervention‐enhanced cancer therapy. [ABSTRACT FROM AUTHOR]

Glycan-mediated interactions play a crucial role in biology and medicine, influencing signalling, immune responses, and disease pathogenesis. However, the use of glycans in biosensing and diagnostics is limited by cross-reactivity, as certain glycan motifs can be recognised by multiple biologically distinct protein receptors. To address this specificity challenge, we report the enzymatic synthesis of a 150-member library of site-specifically fluorinated Lewisx analogues ('glycofluoroforms') using naturally occurring enzymes and fluorinated monosaccharides. Subsequent incorporation of a subset of these glycans into nanoparticles or a microarray revealed a striking spectrum of distinct binding intensities across different proteins that recognise Lewisx. Notably, we show that for two proteins with unique binding sites for Lewisx, glycofluoroforms exhibited enhanced binding to one protein, whilst reduced binding to the other, with selectivity governed by fluorination patterns. We finally showcase the potential diagnostic utility of this approach in glycofluoroform-mediated bacterial toxin detection by lateral flow. Distinguishing between different proteins that each bind to the same type of glycan is challenging. Here, the authors demonstrate that an enzymatically synthesised library of Lewisx 'glycofluoroforms' that feature site-specific fluorination can discriminate closely related proteins. [ABSTRACT FROM AUTHOR]

Decarboxylative cross‐coupling reactions are powerful tools for carbon‐heteroatom bonds formation, but typically require pre‐activated carboxylic acids as substrates or heteroelectrophiles as functional groups. Herein, we present an electrochemical decarboxylative cross‐coupling of carboxylic acids with structurally diverse fluorine, alcohol, H2O, acid, and amine as nucleophiles. This strategy takes advantage of the ready availability of these building blocks from commercial libraries, as well as the mild and oxidant‐free conditions provided by electrochemical system. This reaction demonstrates good functional‐group tolerance and its utility in late‐stage functionalization. [ABSTRACT FROM AUTHOR]

A green and efficient protocol for the direct monofluorination of unactivated alkylarenes under visible‐light irradiation has been developed, without any extraneous transition‐metal catalysts or photosensitizers. This method is compatible with a broad spectrum of functional groups, including carboxylic and alcoholic scaffolds, under mild reaction conditions. Gram‐scale synthesis of a fluorine‐containing pharmaceutical analogue was successfully executed, underscoring the strategy's reliability and practicality. Furthermore, mechanistic studies suggest that a single‐electron transfer mechanism might be responsible for the generation of the benzylic radicals in initiation step. [ABSTRACT FROM AUTHOR]

Chirality‐induced spin selectivity observed in chiral 2D organic–inorganic hybrid perovskite holds promise to achieve spin‐dependent electrochemistry. However, conventional chiral 2D perovskites suffer from low conductivity and hygroscopicity, limiting electrochemical performance and operational stability. Here, a cutting‐edge material design is introduced to develop a stable and efficient chiral perovskite‐based spin polarizer by employing fluorinated chiral cation. The fluorination approach effectively promotes the charge carrier transport along the out‐of‐plane direction by mitigating the dielectric confinement effect within the multi‐quantum well‐structured 2D perovskite. Integrating the fluorinated cation incorporated spin polarizer with BiVO4 photoanode considerably boosts the photocurrent density while reducing overpotential through a spin‐dependent oxygen evolution reaction. Furthermore, the hydrophobic nature of fluorine in spin polarizer endows operational stability to the photoanode, extending the durability by 280% as compared to the device with non‐fluorinated spin polarizer. [ABSTRACT FROM AUTHOR]

S(VI) compounds with multiple N or O substituents are often difficult to make and several crucial routes, such as multimodal SuFEx (Sulfur (VI) Fluoride Exchange) chemistry, rely on the highly useful but hazardous SOF4 gas. Safety issues and inaccessibility of SOF4 strongly hamper the developments of these organic compounds. Here we describe the synthesis and applications of 2‐methylimidazole‐1‐(N‐tert‐octyl)sulfonimidoyl fluoride (ImSF), a novel bench‐stable analogue of SOF4. ImSF is synthesized on a gram scale via a double fluorination of t‐OctNSO. We show ImSF can undergo substitution reactions with phenols and amines, which lead to sulfurimidates and sulfuramidimidates, respectively, the intrinsically chiral analogous of medicinally relevant sulfates and sulfamates in which an S=O moiety is replaced by S=NR unit. Finally we demonstrate that such substitutions can occur enantiospecifically, providing the first entry to chiral sulfurimidates and sulfuramidimidates. [ABSTRACT FROM AUTHOR]

Commercial NH4-Beta and Na-ZSM-5 zeolites were fluorinated with different amounts of NH4F and using different procedures (room temperature, conventional refluxing, microwave refluxing). Samples were characterized by XRD, N2 physisorption, FTIR, 1H NMR, SEM-EDS, and TGA of adsorbed cyclohexylamine. An increase in the concentration of NH4F led to fluorinated zeolites with higher surface areas and slightly lower amounts of Brønsted acid sites due to some dealumination. Fluorination by conventional or microwave refluxing at shorter times did not dealuminate ZSM-5, resulting in the formation of higher particle sizes. Ni/fluorinated beta catalysts were more active than Ni/fluorinated ZSM-5 catalysts for the hydrodeoxygenation of guaiacol at 180 °C and 15 bar of H2 for 1 h due to their higher amount of acid sites. The appropriate proportion of metallic and Brønsted acid centers allowed for the selective obtention of cyclohexane (58%) for the Ni supported on beta fluorinated with NH4F 0.1 M catalyst. The combination of this fluorinated beta to a Ni/ordered mesoporous carbon catalyst significantly boosted its selectivity to cyclohexane from 0 to 65%. Fluorinated ZSM-5 samples, although having stronger Brønsted acid sites, as observed by 1H NMR, they had lower amounts, leading to higher selectivity to cyclohexanol when used as catalytic supports. [ABSTRACT FROM AUTHOR]

The host kinase casein kinase 2 (CSNK2) has been proposed to be an antiviral target against β-coronaviral infection. To pharmacologically validate CSNK2 as a drug target in vivo, potent and selective CSNK2 inhibitors with good pharmacokinetic properties are required. Inhibitors based on the pyrazolo[1,5-a]pyrimidine scaffold possess outstanding potency and selectivity for CSNK2, but bioavailability and metabolic stability are often challenging. By strategically installing a fluorine atom on an electron-rich phenyl ring of a previously characterized inhibitor 1, we discovered compound 2 as a promising lead compound with improved in vivo metabolic stability. Compound 2 maintained excellent cellular potency against CSNK2, submicromolar antiviral potency, and favorable solubility, and was remarkably selective for CSNK2 when screened against 192 kinases across the human kinome. We additionally present a co-crystal structure to support its on-target binding mode. In vivo, compound 2 was orally bioavailable, and demonstrated modest and transient inhibition of CSNK2, although antiviral activity was not observed, possibly attributed to its lack of prolonged CSNK2 inhibition. [ABSTRACT FROM AUTHOR]

Fluorinated ether‐based electrolytes are commonly employed in lithium metal batteries (LMBs) to attenuate the coordination ability of ether solvents with Li+ and induce inorganic‐rich interphase, whereas fluorination inevitably introduces exorbitant production expenses and environmental anxieties. Herein, a non‐fluorinated molecular design strategy has been conceptualized by incorporating methoxy as an electron‐donating group to generate a quasi‐conjugate effect for tuning the affinity of Li+‐solvent, thereby enabling the cyclic ether solvent 2‐methoxy‐1,3‐dioxolane with weak solvation ability and exceptional Li metal‐compatibility. Accordingly, the optimized electrolyte exhibits anion‐dominant solvation structure for inorganic‐rich interphase and fulfills an impressive Li plating/stripping Coulombic efficiency of 99.6 %. As‐fabricated Li||LiFePO4 full cells with limited Li (N/P=2.5) showcase a high capacity retention of 83 % after 150 cycles, indicating excellent cycling stability. Moreover, the full LMBs demonstrate exceptional tolerance towards a wide temperature range from −20 °C to 60 °C, displaying a remarkable capacity retention of 90 % after 110 cycles at −20 °C. Such a molecular design strategy offers a promising avenue for electrolyte engineering beyond fluorination in order to cultivate high‐performance LMBs. [ABSTRACT FROM AUTHOR]

Two new partially fluorinated dehydrobenzannulenes have been prepared by inter‐ and intramolecular oxidative homocoupling of diyne precursors. These systems contain fluorinated and nonfluorinated arene rings in a desymmetrized non‐alternant arrangement. Both macrocycles are roughly planar and organize into extended columns in the solid state. The assembly of these columns is mediated by the combination of dispersion interactions, slipped [π⋅⋅⋅π] stacking interactions of the perfluorinated rings with each other, and their association with the nonfluorinated rings in the molecules of the neighboring macrocycles. These results suggest that partial fluorination of dehydrobenzannulenes can serve as a versatile motif for their assembly into columnar superstructures. [ABSTRACT FROM AUTHOR]

The formation of carbon‐fluorine (C−F) bonds is an important research field in organic synthesis because inserting a fluorine atom into an organic compound can alter its physicochemical properties, such as metabolic stability and permeability. Due to this unique property, organic fluorinated compounds, especially aryl fluorides, have a wide range of applications in various fields, including agrochemicals, pharmaceuticals, and materials science. Therefore, numerous metal‐ or metal‐free‐mediated fluorination reactions have been developed to synthesize aryl fluorides. In this mini‐review, we summarize recent ten years' advances in fluorination reactions for the synthesis of aryl fluorides. [ABSTRACT FROM AUTHOR]

Fluorination of azopyridine N-donors regulates the formation of either B ← N coordination adducts or a co-crystal with phenylboronic acid catechol ester. Specifically, the formation of B ← N adducts is promoted by azopyridines with up to four fluorines, while perfluorination affords a co-crystal via phenyl–perfluoropyridyl [π⋯πF] contacts. Electrostatic potential maps showed supramolecular bonding competition outcomes to be primarily determined by modulation of electron-donating capacity and π surfaces of azopyridine N-donors using fluorination. [ABSTRACT FROM AUTHOR]

All‐polymer solar cells (all‐PSCs) offer promising potential for large‐scale manufacturing due to their remarkable mechanical and thermal stability. However, the limited capacity of polymer acceptors for near‐infrared (NIR) photon harvesting has impeded their progress in semi‐transparent (ST) all‐PSCs. Here, the study develops a pair of new NIR polymer acceptors, named PYSeF‐T and PYSe2F‐T, with mono‐/di‐fluorinated end groups capped to the selenide monomer backbone, respectively. Owing to the stronger intermolecular interaction and intramolecular charge transfer effect of the di‐fluorinated end groups with the selenide backbone, PYSe2F‐T exhibits a stronger crystallinity and a more bathochromic absorption to 1000 nm. When blended with the donor, PM6, the PY2SeF‐T‐based all‐PSC demonstrates a higher efficiency of 16.73% with a remarkable short‐circuit current (JSC) of 27.7 mA cm−2, which is the highest JSC for all‐PSCs. Based on these, the ST device based on PM6:PYSe2F‐T demonstrates a superior efficiency of 12.52% with an average visible transmittance of 26.2% and a light utilization efficiency of 3.28%, outperforming the mono‐fluorinated counterpart. The work provides an in‐depth understanding of the above synergistic effects to develop NIR polymer acceptors and establishes a solid foundation for future investigations into large‐area and flexible ST all‐PSCs. [ABSTRACT FROM AUTHOR]

Separating helium (He) and hydrogen (H2), two gases that are extremely similar in molecular size and condensation properties, presents a formidable challenge in the helium industry. The development of membranes capable of precisely differentiating between these gases is crucial for achieving large‐scale, energy‐efficient He/H2 separation. However, the limited selectivity of current membranes has hindered their practical application. In this study, we propose a novel approach to overcome this challenge by engineering submicroporous membranes through the fluorination of partially carbonized hollow fibers. We demonstrate that the fluorine substitution on the inner rim of the micropore walls within the carbon hollow fibers enables tunability of the microporous architecture. Furthermore, it enhances interactions between H2 molecules and the micropore walls through the polarization and hydrogen bonding induced by C−F bonds, resulting in simultaneous improvements in both He/H2 diffusivity and solubility selectivities. The fluorinated HFM‐550‐F‐1 min membrane exhibits exceptional mixed‐gas separation performance, with a binary mixed‐gas He/H2 selectivity of 10.5 and a ternary mixed‐gas He/(H2+CO2) selectivity of 20.8, at 40 bar feed pressure and 35 °C, surpassing all previously reported polymer‐based gas separation membranes, and remarkable plasticization resistance and long‐term continuous stability over 30 days. [ABSTRACT FROM AUTHOR]

Highlights: By introducing fluorine modulation into MXene, a new MXene-derived material TiOF/Ti3C2 was successfully synthesized with a distinctive three-dimensional structure and a tailored F distribution. In situ characterizations and electrochemical analyses demonstrate that TiOF/Ti3C2 catalysts effectively coupled the multiphase sulfur species conversion processes. The investigations reveal that the theoretical basis of the fluorine catalysis in Li–S batteries originated from Lewis acid–base mechanisms and charge compensation mechanisms. Fluorine owing to its inherently high electronegativity exhibits charge delocalization and ion dissociation capabilities; as a result, there has been an influx of research studies focused on the utilization of fluorides to optimize solid electrolyte interfaces and provide dynamic protection of electrodes to regulate the reaction and function performance of batteries. Nonetheless, the shuttle effect and the sluggish redox reaction kinetics emphasize the potential bottlenecks of lithium–sulfur batteries. Whether fluorine modulation regulate the reaction process of Li–S chemistry? Here, the TiOF/Ti3C2 MXene nanoribbons with a tailored F distribution were constructed via an NH4F fluorinated method. Relying on in situ characterizations and electrochemical analysis, the F activates the catalysis function of Ti metal atoms in the consecutive redox reaction. The positive charge of Ti metal sites is increased due to the formation of O–Ti–F bonds based on the Lewis acid–base mechanism, which contributes to the adsorption of polysulfides, provides more nucleation sites and promotes the cleavage of S–S bonds. This facilitates the deposition of Li2S at lower overpotentials. Additionally, fluorine has the capacity to capture electrons originating from Li2S dissolution due to charge compensation mechanisms. The fluorine modulation strategy holds the promise of guiding the construction of fluorine-based catalysts and facilitating the seamless integration of multiple consecutive heterogeneous catalytic processes. [ABSTRACT FROM AUTHOR]

The development of an efficient alternative to the widely employed Balz‐Schiemann deaminative fluorination method (i. e. without using aryl diazonium tetrafluoroborate salt) is a challenging task. Herein, we report a convenient one‐pot method for the FeCl3‐nanocellullose mediated mechanochemical synthesis of fluoroarenes through the selective substitution of an aromatic amino group by fluorine group using pyrylium tetrafluoroborate (Pyry‐BF4) and sodium fluoride (NaF) via in situ formation of pyridinium salt intermediate. The scope of the present protocol includes synthesis of thirty‐four organofluorine compounds with excellent yields via a selective substitution (SNAr) of an amino group by fluorine. The presented concise methodology opens a pathway to access new chemical spaces for the late‐stage functionalization in pharmaceutical industries. [ABSTRACT FROM AUTHOR]

Inspired by C–H hydroxylation by cytochrome P450 enzymes (P450s), we report here a method for preparing organofluorides through a single-electron transfer (SET) process, in which the pyridine N-oxyl radical greatly promotes the C–H fluorination. This reaction can be carried out in pure water at room temperature and accommodates a wide range of substrates, including bioactive molecules, with good yields. Mechanistic investigations indicate that reactions advance through radical intermediates. [ABSTRACT FROM AUTHOR]

Fluorination of heterocyclic compounds accompanied by molecular rearrangements is an area of synthesis experiencing rapid advances. One of the characteristics of electrophilic and oxidative fluorination is the involvement of carbocations, radicals, and radical ions which can undergo rearrangements. Such rearrangements expand the range of fluorinated products, which are sometimes difficult to access by direct fluorination of heterocyclic compounds. The purpose of this review is to systematize and analyze the literature data published over the past decade on fluorination of heterocyclic compounds accompanied by molecular rearrangements. Particular attention is paid to the analysis of reaction mechanisms and the problem of selectivity. [ABSTRACT FROM AUTHOR]

Recently, we suggested liquid and high‐boiling TIPS‐CC‐SF5 (TASP) as a versatile reagent to access so far elusive SF5‐containing building blocks by less specialized laboratories under bench‐top conditions. The synthesis of non‐aromatic SF5 building blocks generally requires on‐site fluorination or pentafluorosulfanylation steps employing toxic and/or gaseous reagents. Herein, we underline the versatility of this reagent by reporting a benign bench‐top protocol for the synthesis of Z‐configured β‐pentafluorosulfanylated vinyl sulfides in good to excellent yields (up to 99 %) with exclusive (Z)‐diasteroselectivity and broad functional group tolerance. This method exploits an in‐situ protodesilylation‐hydrothiolation sequence. This so far uncharted class of compounds was characterized by means of NMR‐spectroscopy as well as SC‐XRD. Furthermore, we suggest the reaction to proceed via a kinetically controlled closed‐shell reaction pathway, corroborated by in‐silico experiments. [ABSTRACT FROM AUTHOR]

B(C6F5)3 and the corresponding anion [B(C6F5)4]− are ubiquitous in main group and transition metal chemistry. Known derivatives are generally limited to the incorporation of electron donating substituents. Herein we describe electrophilic fluorination and dearomatization of such species using XeF2 in the presence of BF3 or Lewis acidic cations. In this fashion the anions [HB(C6F5)3]−, [B(C6F5)4]− and [(C6F5)3BC≡NB(C6F5)3]−, are converted to [FB(C6F7)3]−, [B(C6F7)4]−, and [(C6F7)3BC≡NB(C6F7)3]−, respectively. Similarly, the borane adducts (L)B(C6F7)3 (L=MeCN, OPEt3) are produced. These rare examples of electrophilic attack of electron deficient rings proceed as [XeF][BF4] acts as a frustrated Lewis pair effecting fluorination and dearomatization of C6F5 rings. [ABSTRACT FROM AUTHOR]

Nucleophilic fluorination of aromatic rings can be done via a cross-coupling reaction catalyzed by palladium and biaryl monophosphine ligands such as AlPhos. Nevertheless, aromatic fluorination via palladium catalysis can lead to regioisomers, a serious problem for this kind of reaction. An ortho-deprotonation mechanism was proposed for this reaction in previous studies. However, this mechanism does not explain why the ortho product is not formed from para and meta substrates, and the details of the mechanism are not fully understood yet. This theoretical work discloses the mechanism behind regioisomers formation, which takes place via unimolecular ortho-elimination of HF. The computed free energy profile of the reaction was followed by a detailed microkinetic analysis, which explain the experiments quantitatively. The present study shows that the rotation of the aryne coordinated to the palladium to form a complex leading to the ortho product is critical for regioselectivity. This rotation has a high free energy barrier due to steric repulsion with the adamantane group of the ligand. Such a feature impedes the formation of ortho product from para and meta substrates and allows the formation of the ortho product selectively from the ortho substrate. [ABSTRACT FROM AUTHOR]

The primary objective of this work is to delve into the intricacies of allylic fluorination reactions through the application of density functional theory (DFT) calculations. These reactions hold significant importance in the realm of synthesizing organofluorine compounds. The specific focus lies on comprehending the interaction mechanisms when styrenes, a class of organic molecules, come in contact with an electrophilic fluorinating reagent known as Selectfluor. Notably, this interaction pathway demonstrates remarkable efficiency in yielding allylic fluoride products. The proposed mechanism for this transformation involves a sequential process. To unveil the microcosmic intricacies governing this reaction between the alkene substrate and Selectfluor, advanced computational methodologies are employed. The paper systematically outlines the computational strategies harnessed to probe the minute details of the reaction mechanism. The outcomes of these computations are subsequently subjected to thorough analysis, encompassing crucial facets such as transition states and energy barriers. This analytical depth enhances the fundamental understanding of the reaction mechanism and sheds light on the underlying factors influencing its feasibility and efficiency. In a broader context, the insights garnered from this study carry significant utility. They provide pivotal guidance for the optimization of reaction conditions, facilitating the fine-tuning of experimental setups. Moreover, the elucidated mechanism serves as a platform for the design of even more efficient and selective allylic fluorination reactions. This paper, by amalgamating theoretical insights with practical synthetic objectives, contributes to the broader advancement of organofluorine compound synthesis and allied fields. [ABSTRACT FROM AUTHOR]

Highlights By introducing fluorine modulation into MXene, a new MXene-derived material TiOF/Ti3C2 was successfully synthesized with a distinctive three-dimensional structure and a tailored F distribution. In situ characterizations and electrochemical analyses demonstrate that TiOF/Ti3C2 catalysts effectively coupled the multiphase sulfur species conversion processes. The investigations reveal that the theoretical basis of the fluorine catalysis in Li–S batteries originated from Lewis acid–base mechanisms and charge compensation mechanisms.

Three non-fullerene acceptors (NFAs) with varying alkyl chain sizes and lengths but constant fluorine atoms were synthesized. BO-17F and HD-17F, with optimal fluorination, exhibit improved molecular packing and morphology, achieving efficiencies of 14.2% and 14.4%. This work highlights the importance of fine-tuning alkyl chains and fluorination levels in organic solar cells. [ABSTRACT FROM AUTHOR]

The ability to investigate hypervalent iodine(V) fluorides has been limited primarily by their difficult preparation traditionally using harsh fluorinating reagents such as trifluoromethyl hypofluorite and bromine trifluoride. Here, we report a mild and efficient route using Selectfluor to deliver hypervalent iodine(V) fluorides in good isolated yields (72–90%). Stability studies revealed that bicyclic difluoro(aryl)-λ5-iodane 6 was much more stable in acetonitrile-d3 than in chloroform-d1, presumably due to acetonitrile coordinating to the iodine(V) centre and stabilising it via halogen bonding.

The selective fluorination of C(sp3)–H bonds is an attractive target, particularly for pharmaceutical and agrochemical applications. Consequently, over recent years much attention has been focused on C(sp3)–H fluorination, and several methods that are selective for benzylic C–H bonds have been reported. These protocols operate via several distinct mechanistic pathways and involve a variety of fluorine sources with distinct reactivity profiles. This review aims to give context to these transformations and strategies, highlighting the different tactics to achieve fluorination of benzylic C–H bonds.

This study examined the kinetics of the reaction between tellurium oxide (TeO2) and fluorine gas (F2) to produce tellurium hexafluoride gas (TeF6). This investigation was conducted between 150 and 250 °C and between 1 and 2 bar of pressure. To achieve this, a volumetric method was utilized for the design and constructionof a laboratory system. The supply of feed gases, the fluorination reactor, and the collection and removal of the unreacted gases constitute the three primary components of this laboratory system. To obtain the kinetic parameters, the Arrhenius form of the reaction rate was used. The results obtained indicate that the fluorination reaction of tellurium oxide is a first-order reaction between 150 and 200 °C and a second-order reaction at 250 °C. The AARE values were calculated as 0.57% and 0.46%, respectively, which indicates the excellent capability of kinetic models to predict the reaction kinetics of TeF6 gas production.

The photovoltaic performance of inverted perovskite solar cells (PSCs) is often hindered by trap‐induced non‐radiative recombination and photochemical degradation occurring at the upper interfaces and the grain boundaries of perovskite films. Herein, ortho‐, meta‐, and para‐isomers of fluorophenylethylammonium iodine (F‐PEAI) organic spacer molecules are evaluated for the construction of perovskite quantum wells (2D or quasi‐2D, PQWs) to encapsulate 3D perovskites. Among the three variants, p‐F‐PEAI leads to the most symmetric charge distribution and the weakest steric hindrance which resulting in reinforced interactions with PbI2 and perovskite, the enhanced out‐of‐plane orientation is confirmed by Grazing incidence wide‐angle X‐ray scattering (GIWAXS) results. Density functional theory and crystal orbital Hamilton population (COHP) calculations further confirm that p‐F‐PEAI engages most strongly with the perovskite structure. Moreover, transmission electron microscopy (TEM) characterization is used to illustrate that p‐F‐PEAI‐assisted 2D PQWs effectively passivate both the grain boundaries and surfaces of perovskites. This configuration facilitates effective surface passivation, improves charge carrier transport, and significantly suppresses non‐radiative recombination. The resultant inverted PSCs achieve an excellent power conversion efficiency (PCE) of 25.03% with a fill factor (FF) of 85.11%. The unencapsulated devices exhibit enhanced long‐term stability under ambient environments and continuous light illumination. [ABSTRACT FROM AUTHOR]

A low‐thermal‐budget fabrication approach is developed to realize high‐performance fluorine‐doped indium oxide (In2O3:F) thin‐film transistors (TFTs) with remarkable bias‐stress stability. The ultrathin transistor channel layer is prepared by a re‐developed atomic layer deposition (ALD) process of using cyclopentadienyl indium(I) (InCp) and O2 plasma to deposit a crystalline In2O3 film, followed by a new fluorine doping strategy to use CF4 plasma to afford the In2O3:F layer. As revealed by the density functional theory (DFT) analysis, the fluorine doping can stabilize the lattice oxygen and electrically passivate the problematic VO defects in In2O3 by forming the FOFi spectator defects. Therefore, the fabricated In2O3:F TFTs show simultaneously excellent electrical performance and remarkable bias‐stress stability, with high µFE of 35.9 cm2 V−1 s−1, positive Vth of 0.36 V, steep SS of 94.3 mV dec−1, small hysteresis of 33 mV, and small ΔVth of −111 and 49 mV under NBS and PBS, respectively. This work demonstrates the high promise of the fluorinated ALD In2O3:F TFTs for the CMOS back‐end‐of‐line (BEOL) compatible technologies toward advanced monolithic 3D integration. [ABSTRACT FROM AUTHOR]

Solid electrolyte interphase (SEI) crucially affects the rate performance and cycling lifespan, yet to date more extensive research is still needed in potassium‐ion batteries. We report an ultra‐thin and KF‐enriched SEI triggered by tuned fluorinated surface design in electrode. Our results reveal that fluorination engineering alters the interfacial chemical environment to facilitate inherited electronic conductivity, enhance adsorption ability of potassium, induce localized surface polarization to guide electrolyte decomposition behavior for SEI formation, and especially, enrich the KF crystals in SEI by self‐sacrifice from C−F bond cleavage. Hence, the regulated fluorinated electrode with generated ultra‐thin, uniform, and KF‐enriched SEI shows improved capacity of 439.3 mAh g−1 (3.82 mAh cm−2), boosted rate performance (202.3 mAh g−1 at 8.70 mA cm−2) and durable cycling performance (even under high loading of ~8.7 mg cm−2). We expect this practical engineering principle to open up new opportunities for upgrading the development of potassium‐ion batteries. [ABSTRACT FROM AUTHOR]

Studies have shown that the incorporation of fluorine into materials can improve their properties, but C–F bonds are not readily formed in nature. Although some researchers have studied the reaction of fluorinating alkenes catalyzed by hypervalent iodine, far too little attention has been paid to its reaction mechanism. This study aimed to explore the mechanism of the hypervalent iodine-catalyzed 1,4-difluorination of dienes. We found that the catalyst is favorable for the activation of C1=C2 double bonds through halogen bonds, and then two HFs interact with one F atom in the catalyst via hydrogen bonds, resulting in the cleavage of I–F bonds and the formation of [F–H∙∙∙F]−. Subsequently, the catalyst interacts with C1, and the roaming [F–H···F]− attacks C4 from the opposite side of the catalyst. After the fluorination step is completed, the nucleophile F− substitutes the catalyst via the SN2 mechanism. Our calculations demonstrated that the interaction between HF and F− is favorable for the stabilization of the transition state within the fluorination process for which the presence of two HFs in the reaction is the best. We also observed that [F–H∙∙∙F]− attacking C4 from the opposite side of the catalyst is more advantageous than attacking from the same side. This study therefore offers a novel perspective on the mechanism of the hypervalent iodine-catalyzed fluoridation of dienes. [ABSTRACT FROM AUTHOR]

[Display omitted] The construction of metal–organic frameworks (MOFs) with highly efficient capture for volatile organic compounds (VOCs) adsorption under humid conditions is a significant yet formidable task. Herein, series of fluorinated UiO-67 modified with trifluoroacetic acid (TFA) and 4-fluorobenzoic acid were successfully synthesized for VOCs adsorption under high humidity conditions. Experiments results showed that UiO-67 modified with 4-fluorobenzoic acid (67-F) presented excellent adsorption capacity of 345 mg/g for toluene adsorption and exhibited great water resistance (10.0 vol% H 2 O, 374 mg/g toluene adsorption capacity). Characterization results indicated that the introduction of 4-fluorobenzoic acid induced the competitive coordination between 4-fluorobenzoic acid and 4,4-biphenyl dicarboxylic acid (BPDC) with Zr4+, causing the formation of abundant defects to provide extra adsorption sites. Meanwhile, the benzene ring in 4-fluorobenzoic acid enhanced the π-π conjugation, causing the further promotion of VOCs adsorption capacity. More importantly, the water resistance mechanism was investigated and elucidated that the introduction of F decreased the surface energy of 67-F and its affinity with water. Meanwhile, the metal complex induced by the fluorinated modification produced an electron-dense pore environment, which greatly improved its chemical and water stability. This work provided a strategy for preparing an adsorbent with high water resistance for real-world VOCs adsorption at high humidity conditions. [ABSTRACT FROM AUTHOR]

In this study, a superhydrophobic surface was successfully prepared on Al alloy 5052 using a simple anodic oxidation method followed by fluorination treatment. This study demonstrates the construction of rough structure of Al oxide by an anodic oxidation reaction, which improves the superhydrophobicity of the alloy. The top, tilt, and cross‐views of the samples were characterized by field‐emission scanning electron microscopy and focused ion beam. The chemical composition of the samples was analyzed by energy‐dispersive X‐ray spectroscopy and Fourier‐transform infrared spectroscopy. The structure of the surface was effectively modified as the anodization time increased. The optimum anodic oxidation reaction was carried out for 4 min in a 0.2‐M H3PO4 aqueous electrolyte at 50°C under a constant voltage of 120 V to create a pore‐and‐dendrite hybrid nanostructure. The water contact angle values were maximized in the hybrid nanostructure because their solid fraction area was smaller than that in the porous structure. Corrosion measurements proved that the superhydrophobic surface can significantly inhibit the corrosion of the substrate alloy with an inhibition efficiency of 99.99%. In addition, the prepared superhydrophobic sample exhibited good self‐cleaning properties. [ABSTRACT FROM AUTHOR]

The use of hole transporting material (HTM) remains indispensable for efficient charge extraction in perovskite solar cells. In this work, a series of small-molecule HTMs are designed by introducing fluorine atoms into the central part of 2,2′-bithiophene core. The effect of fluorination on the photophysical, electrochemical, and hole transport properties is systematically explored using Quantum chemistry calculation. The Calculated results reveal that all the highest occupied molecular orbitals (HOMOs) and the lowest unoccupied molecular orbitals (LUMOs) of the studied molecules are well matched with the energy band structure of perovskite. Three fluorine substituted hole-transporting materials possess lower reorganisation energy than the reference molecule BT-MTP. The higher mobility and matched energy levels of predicted HTMs are beneficial for improving the performance of PSCs. All the designed HTMs display higher hole mobility than those of the BT-MTP. Especially, molecule DFBT-p-MTP exhibits better optical properties and stability, indicating that fluorination is an effective strategy to improve the performance of the device in real application. This work provides an avenue for designing low-cost small molecule HTMs for high-performance perovskite solar cells. A series of fluorine substituted hole transporting materials are explored to reveal the relationship between the charge-transport properties and molecular engineering. [ABSTRACT FROM AUTHOR]

Extensive efforts have been made to pursue a low-friction state with promising applications in many fields, such as mechanical and biomedical engineering. Among which, the load capacity of the low-friction state has been considered to be crucial for industrial applications. Here, we report a low friction under ultrahigh contact pressure by building a novel self-assembled fluorinated azobenzene layer on an atomically smooth highly-oriented pyrolytic graphite (HOPG) surface. Sliding friction coefficients could be as low as 0.0005 or even lower under a contact pressure of up to 4 GPa. It demonstrates that the low friction under ultrahigh contact pressure is attributed to molecular fluorination. The fluorination leads to effective and robust lubrication between the tip and the self-assembled layer and enhances tighter rigidity which can reduce the stress concentration in the substrate, which was verified by density functional theory (DFT) and molecular dynamics (MD) simulation. This work provides a new approach to avoid the failure of ultralow friction coefficient under relatively high contact pressure, which has promising potential application value in the future. [ABSTRACT FROM AUTHOR]

The electrolyte stability under high‐voltage conditions considerably limits the upper cut‐off potential of solid‐state electrolytes (SSEs) and therefore the energy density of all‐solid‐state batteries (ASSBs). In this work, metal‐organic frameworks (MOFs) were fluorinated to lower the energy level of HOMO orbital and allow access to a 4F‐MOF that exhibit enhanced anodic stability. The composited 4F‐MOF/PEO electrolyte could not only transport Li+ ions in the ordered framework channels, but also provide a remarkable high‐voltage stability up to 5.0 V, shielding oxidative decomposition that would otherwise occur at around 3.9 V for conventional PEO electrolytes. In addition, stable lithium deposition was demonstrated for more than 1,300 hours at 0.1 mA ⋅ cm−2, while reversible charge‐discharge cycling performance was delivered in assembled Li||LiNi0.5Mn1.5O4 (LNMO) ASSBs up to 5.0 V. Post‐mortem X‐ray photoelectron spectroscopy (XPS) investigation on cathodes revealed presence of a LiF‐rich cathode electrolyte interface (CEI), supporting promoted stability towards high‐voltage ASSBs. [ABSTRACT FROM AUTHOR]

The fluorinated 5‐membered N‐containing heterocyclic compounds have wide utility in varied fields. The importance of these compounds has encouraged researchers to explore environment‐friendly synthetic techniques for their synthesis. In this context, microwave‐assisted synthesis has proved beneficial for the synthesis of fluorinated 5‐membered N‐heterocycles in an environmentally benign and energy‐efficient manner. Compared to conventional heating, it offers several advantages, including quick heating, short reaction times, higher yields, and fewer side reactions. This article highlights the microwave‐assisted fluorination of 5‐membered N‐heterocyclic compounds along with the synthesis of fluorinated 5‐membered N‐heterocyclic compounds using fluorinated starting materials. [ABSTRACT FROM AUTHOR]

Fluorinated non‐natural amino acids are attracting considerable research interest, especially in the biomedical field and in materials science, thanks to their ability to self‐assemble into peculiar supramolecular structures. The conformational changes induced by the presence of fluorine atoms obviously affect their functions, as well as the biological activity of the deriving peptides and proteins. Here, we will briefly describe the main effects of fluorination on the aggregation behavior of such building blocks, focusing in particular on their improved tendency to form fibrils, and gels therefrom. Our aim is to underline the promising potential of fluorination as a tool to affect the self‐assembly features of amino acids, both when used alone and when inserted into polypeptide sequences. The ability of fluorine to influence physical, chemical, and structural properties of these substrates offers the possibility to engineer bioinspired materials with specific and tunable functions. [ABSTRACT FROM AUTHOR]

Solid electrolytes (SEs) have the potential to enhance the safety and performance of Li‐metal batteries. However, the existence of grain boundaries in polycrystalline SEs presents a significant challenge for both ionic and electronic migration, promoting the propagation of detrimental lithium dendrites. This study compares the roles of grain boundaries in electrical properties of three distinct SEs including garnet‐type Li6.5La3Zr1.5Ta0.5O12 (LLZO), argyrodite‐type Li6PS5Cl (LPSC), and NASICON‐type Li1+x+yAlx(Ti,Ge)2‐xSiyP3‐yO12 (LATP). Results demonstrate that the electronic and ionic conductivities of solid‐state electrolytes are affected differently by grain boundaries, depending on the specific type of electrolyte. For instance, LLZO and LATP experience dielectric breakdown at 3.7 and 5.3 V, respectively, while LPSC does not exhibit such behavior. Here, a new chemical modification is proposed that simultaneously alters the composition of both the surface and grain boundaries of SEs, ultimately reducing electronic conductivity for the LLZO SEs. Consequently, the proposed LLZO exhibits unprecedented dendrite‐free cycling stability, achieving a remarkable 12 000‐h lifetime at room temperature, surpassing conventional strategies such as surface coatings in dendrite mitigation. This study highlights the significance of modifying grain boundaries to design safe and durable Li‐metal batteries. It provides new insights for developing SEs that are highly resistant to dendrite formation. [ABSTRACT FROM AUTHOR]

In order to prepare self-standing and flexible slow neutron reflectors made of graphite fluoride (GF) with high contents of (C2F)n structural phase, graphite foils of different thicknesses were used as starting materials for gas (F2)/solid fluorination. The maximal interlayer distance of GF was obtained with this phase thanks to the stacking sequence FCCF/FCCF; this is mandatory for the efficient reflection of slow neutrons. 71 and 77% of the (C2F)n phase were achieved for graphite foils with thicknesses of 1.0 and 0.1 mm, respectively. The interlayer distances were 8.6 Å as expected. The fluorination conditions (static mode, a long duration of 24 h, annealing in pure F2 gas for 24 h, and temperatures in the 390–460 °C range) were adapted to large pieces of graphite foils (7 × 7 cm2) in order to both avoid exfoliation and achieve a homogeneous dispersion of fluorine atoms. This process was also efficient for thinner (0.01 mm thick) graphitized graphene oxide foil. 56% of the (C2F)n phase and an interlayer of 8.6 Å were achieved for this foil when fluorination was performed at 430 °C. Whatever the nature and the thickness of the foil, their flexibilities are maintained. [ABSTRACT FROM AUTHOR]

Herein, we synthesized two donor‐acceptor (D‐A) type small organic molecules with self‐assembly properties, namely MPA‐BT‐BA and MPA‐2FBT‐BA, both containing a low acidity anchoring group, benzoic acid. After systematically investigation, it is found that, with the fluorination, the MPA‐2FBT‐BA demonstrates a lower highest occupied molecular orbital (HOMO) energy level, higher hole mobility, higher hydrophobicity and stronger interaction with the perovskite layer than that of MPA‐BT‐BA. As a result, the device based‐on MPA‐2FBT‐BA displays a better crystallization and morphology of perovskite layer with larger grain size and less non‐radiative recombination. Consequently, the device using MPA‐2FBT‐BA as hole transport material achieved the power conversion efficiency (PCE) of 20.32 % and remarkable stability. After being kept in an N2 glove box for 116 days, the unsealed PSCs' device retained 93 % of its initial PCE. Even exposed to air with a relative humidity range of 30±5 % for 43 days, its PCE remained above 91 % of its initial condition. This study highlights the vital importance of the fluorination strategy combined with a low acidity anchoring group in SAMs, offering a pathway to achieve efficient and stable PSCs. [ABSTRACT FROM AUTHOR]

The electroreduction of carbon dioxide (CO2) to multi‐carbon (C2+) compounds offers a viable approach for the up‐conversion of greenhouse gases into valuable fuels and feedstocks. Nevertheless, current industrial applications face limitations due to unsatisfactory conversion efficiency and high overpotential. Herein, a facile and scalable plasma fluorination method is reported. Concurrently, self‐evolution during CO2 electroreduction is employed to control the active sites of Cu catalysts. The copper catalyst modified with fluorine exhibits an impressive C2+ Faradaic efficiency (FE) of 81.8% at a low potential of −0.56 V (vs a reversible hydrogen electrode) in an alkaline flow cell. The presence of modified fluorine leads to the exposure and stabilization of high‐activity Cu+ species, enhancing the adsorption of *CO intermediates and the generation of *CHO, facilitating the subsequent dimerization. This results in a notably improved conversion efficiency of 13.1% and a significant reduction in the overpotential (≈100 mV) for the C2+ products. Furthermore, a superior C2+ FE of 81.6% at 250 mA cm−2, coupled with an energy efficiency of 31.0%, can be achieved in a two‐electrode membrane electrode assembly electrolyzer utilizing the fluorine‐modified copper catalyst. The strategy provides novel insights into the controllable electronic modification and surface reconstruction of electrocatalysts with practical potential. [ABSTRACT FROM AUTHOR]

Li(Ni0.80Co0.15Al0.05)O2 is a lithium-ion battery cathode, commercially available for more than twenty years, which is associated with high energy capacity and high energy density, with moderate power. Atomic layer fluorination (ALF) of Li(Ni0.80Co0.15Al0.05)O2 with XeF2 is performed to improve its cyclability. The ALF method aims at forming an efficient protecting fluorinated layer at the surface of the material, with a low fluorine content. Surface fluorinated Li(Ni0.80Co0.15Al0.05)O2 is characterized by X-ray diffraction, electron microscopy, 19F nuclear magnetic resonance, X-ray photoelectron spectroscopy, and galvanostatic measurements, and a fluorine content as low as 1.4 wt% is found. The presence of fluorine atoms improves the electrochemical performances of Li(Ni0.80Co0.15Al0.05)O2: cyclability, polarization and rate capability are improved. Operando infrared spectroscopy and post-mortem gas chromatography provide some insights into the origins of these improvements. [ABSTRACT FROM AUTHOR]