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Herein, we demonstrate a method for the syntheses of sulfinamides and sulfinate esters using a novel sulfur(IV) fluoride exchange reaction with organometallic reagents. Our strategy involves the addition of an amine or alcohol nucleophile to thionyl fluoride, acting as a S(IV) SuFEx hub, followed by an organometallic reagent. This approach allows efficient access to sulfinamides (45–91% yields) and sulfinate esters (44–82% yields) in only 30 minutes. The sulfinamide and sulfinate esters also can be readily derivatized to the corresponding S(VI) sulfonamides, sulfonate esters, sulfonimidamides, and sulfonimidates without isolation of the intermediates. [ABSTRACT FROM AUTHOR]

We describe a palladium-catalyzed Suzuki-type cross-coupling reaction of 2-pyridyl carbamoyl fluorides with boronic acids, which provides entry to medicinally relevant pyridyl amides. Mechanistic studies, including the synthesis and reactivity of carbamoyl Pd–F complexes, reveal the importance of both the fluoride electrophile and nitrogen directing group for aiding reactivity. [ABSTRACT FROM AUTHOR]

We report a new class of degradable fluorinated polymers through the copolymerization of tetrafluorophthalic anhydride and propylene oxide or trifluoropropylene oxide which show up to 20 times quicker degradation than the non-fluorinated equivalents and allow for fluoride recovery. [ABSTRACT FROM AUTHOR]

In this study, a solid-state ion exchange (SSIE) method is proposed to synthesize a series of Mn4+-doped fluoride phosphors, which avoids the use of HF solution during the Mn4+-doping process. The obtained Mn4+-doped fluoride phosphors exhibit strong red emission with a quantum yield of 46%. [ABSTRACT FROM AUTHOR]

The article discusses a method for synthesizing amide bonds using deoxyfluorinated carboxylic acids and pyridinesulfonyl fluoride. The authors optimized the reaction conditions and explored the substrate scope, demonstrating the versatility and utility of their method. They also showcase the application of this methodology in the synthesis of a challenging ester-linked compound and a tetrapeptide. The research was supported by various funding sources, and there are no conflicts of interest to declare. This article provides valuable information for researchers in the field of medicinal chemistry and organic synthesis. [Extracted from the article]

Herein, we report an easily oxidized Co–Fe perovskite fluoride as an efficient catalyst for the oxygen evolution reaction (OER). In situ Raman spectroscopy showed that the presence of F promotes reconstruction to form highly active (Co3+Fe3+)OOH, and the current density of 10 mA cm−2 can be achieved at the overpotential of only 118 mV in 1 M KOH aqueous solution. This work helps to understand the role of fluoride during the OER. [ABSTRACT FROM AUTHOR]

The new bis(alkynyl)mercurial Hg{C≡CSeC≡W(CO)2(Tp*)}2 (Tp* = tris(dimethylpyrazolyl)borate) forms adducts with fluoride and phenathroline, the structures of which are interpreted in the context of two-coordinate mercury presenting a σ-torroid for spodium bonding. [ABSTRACT FROM AUTHOR]

Sol–gel transition regulates mass transport in fluidic systems. We designed pre-gelators that react with fluoride anions to form a metallogel barrier. A combination of spectroscopic, rheological, and X-ray spectroscopic studies elucidated the mechanism of gelation involving desilylation followed by metal coordination-driven self-assembly, the kinetics of which can be finely controlled by the chemical structure of the silyl substituents. Protonation-induced degelation restores flow, allowing the metallogel to function as a reversible chemical valve. [ABSTRACT FROM AUTHOR]

A practical method that enables the fluorosulfenylation of unactivated alkenes processed directly with thiols and fluoride salts is presented. Good to excellent efficiencies and functional group tolerance are observed for both alkene substrates and thiols. The procedure also allows the use of gaseous ethylene as a two-carbon building block for β-fluoro thioether products. [ABSTRACT FROM AUTHOR]

Meso-3,5-bis(trifluoromethyl)phenyl picket calix[4]pyrrole 1 displays excellent fluoride anion transport activity across artificial lipid bilayers showing EC50 = 2.15 μM (at 450 s in EYPC vesicle) with high fluoride over chloride ion selectivity. The high fluoride selectivity of 1 was ascribed to the formation of a sandwich type π-anion-π interaction complex. [ABSTRACT FROM AUTHOR]

We report a mild, electrochemical trihydrodefluorination (e-THDF) for breaking highly stable C–F bonds in trifluoromethyl arenes to form the corresponding methyl arene products. Uniquely, this "green" approach relies on the in situ generation of Lewis acidic silyl cations that mediate fluoride abstraction. Overall, e-THDF has significantly improved functional group tolerance over current methods and should inspire the continued development of defluorinative processes. [ABSTRACT FROM AUTHOR]

Here we present a new method to monitor fluoride transmembrane transport into liposomes using a europium(III) complex. We take advantage of the long emission lifetime of this probe to measure the transport activity of a fluorescent transporter. The high sensitivity, selectivity, and versatility of the assay allowed us to study different types of fluoride transporters and unravel their mechanisms of action. [ABSTRACT FROM AUTHOR]

Triarylborane-based discrete metal-carbene supramolecular cages [M3(1)2](PF6)3 (M = Ag, Au) were synthesized and characterized. The new hexacarbene assemblies show a significant solvatochromic effect in solvents of different polarity. Furthermore, the reversible fluoride binding property of [Au3(1)2](PF6)3 was investigated by UV-vis absorption and fluorescence titrations. This work holds promise for future developments in the area of highly emissive and stimulus-responsive NHC-metal assemblies. [ABSTRACT FROM AUTHOR]

A pure silica STW zeolite is synthesized with no impurities under a wide range of synthesis conditions with and without fluoride by using easily available 1-methyl-1,5-diazabicyclo[4.3.0]non-5-ene (MDBN) as a template. MDBN having an appropriate size and geometry fits well in the STW cage, leading to its high specificity in structure-directing formation of zeolite STW. [ABSTRACT FROM AUTHOR]

A quinoxaline-fused octaphyrin(2.0.0.0.2.0.0.0) was synthesized by the FeCl3-induced oxidative coupling of an α-free quinoxaline-fused tetrapyrrole. This macrocycle adopts a figure-of-eight conformation in the solid state and acts as a rudimentary chemosensor in solution. The Lewis basic anions fluoride and hydroxide induce a colour change via a deprotonation mechanism. [ABSTRACT FROM AUTHOR]

Herein, we demonstrate two complementary strategies for the syntheses of sulfonyl fluorides using sulfonic acids and their salts. One strategy involves the conversion of sulfonic acid sodium salts to sulfonyl fluorides using thionyl fluoride in 90–99% yields in one hour. Lessons learned from the mechanism of this reaction also have enabled a complementary deoxyfluorination of sulfonic acids using Xtalfluor-E® – a bench stable solid – allowing for the conversion of both aryl and alkyl sulfonic acids and salts to sulfonyl fluorides in 41–94% yields. Notably, using Xtalfluor-E® enabled milder conditions and the use of both sulfonic acids and their sodium salts. [ABSTRACT FROM AUTHOR]

We report a new concept for the turn-on fluoride sensor based on the aggregation of dye-modified polyhedral oligomeric silsesquioxane (POSS). The dye-modified POSS aggregation initially shows weak fluorescence, while intense fluorescence can be obtained when fluoride breaks POSS cores following dye release. [ABSTRACT FROM AUTHOR]

In order to expand the toolbox of enzymes available for thioglycoside synthesis, we describe here the first example of an extremophilic glycosyl hydrolase from Halothermothrix orenii (HorGH1) engineered towards thioglycosynthase activity with a novel combination of mutations. Using the triple mutant, HorGH1 M299R/E166A/E354G, a range of thioglycosides from glycosyl fluoride donors and aromatic thiols could be synthesised with exquisite stereoselectivity and good to excellent conversions (61–93%). [ABSTRACT FROM AUTHOR]

A novel strategy for the synthesis of 2-arylethenesulfonyl fluorides from nitrones and ethenesulfonyl fluoride (ESF) by the activation of the C–H bond using an inexpensive and readily available Ru-catalyst has been developed. In this process, the directing group can be concomitantly converted to an amide group. Interestingly, changing the substituent of the nitrogen of nitrones from a tert-butyl to a methyl group resulted in the formation of cyclic isoindolinones. Detailed mechanistic studies are also presented. [ABSTRACT FROM AUTHOR]

We report on two different sets of air-stable derivatives of pentafluoroorthotellurate containing fluorinated and non-fluorinated aryl groups. The acid cis-PhTeF4OH was obtained in gram scale and further transformed to Ag[cis-PhTeF4O], which was used as a cis-PhTeF4O transfer reagent to obtain [PPh4][cis-PhTeF4O]. Furthermore, the synthesis of trans-(C6F5)2TeF3OH was achieved by a selective hydrolysis of trans-(C6F5)2TeF4 in the presence of KF and subsequent protonation by aHF. Quantum-chemical calculations show a higher acidity and robustness against fluoride abstraction for trans-(C6F5)2TeF3OH compared to cis-PhTeF4OH. [ABSTRACT FROM AUTHOR]

Real-time in situ temperature sensing is of significance in the bio-medical field; however, the low relative temperature sensitivity Sr is one of the major obstacles in the development of nanothermometers. Herein, we provide an effective route that engineers the interfacial layer in a core/shell/shell nanostructure to enlarge the temperature-dependent luminescence intensity ratio (LIR) variations followed by an improved Sr. The CaF2 interlayer is employed to inhibit the interaction between the core and outer shell, and increase the interfacial phonon energy to enhance the negative thermal quenching effect (TQE) of Nd3+ ions in the outer shell and positive TQE of Er3+ ions in the core layer. Based on the temperature-dependent LIR variations of Er (650 nm) to Nd (800 nm), the maximum Sr of 10.01% K−1 and minimum Sr of % 2.56% K−1 are achieved. [ABSTRACT FROM AUTHOR]

Sulfonimidoyl halides have previously shown poor stability and selectivity in reaction with organometallic reagents. Here we report the preparation of enantioenriched sulfonimidoyl fluorides and their stereospecific reaction at sulfur with Grignard reagents. Notably the first enantioenriched alkyl sulfonimidoyl fluorides are prepared, including methyl. The nature of the N-group is important to the success of the stereocontrolled sequence to sulfoximines. [ABSTRACT FROM AUTHOR]

A Cu-catalysed borylation of aryl alkyl sulfones was developed for the high yield synthesis of versatile arylboronic esters using a readily prepared NHC–Cu catalyst. In addition, the selective cleavage of either alkyl(C)–sulfonyl or aryl(C)–sulfonyl bonds of a cyclic sulfone via Cu-free or Cu-mediated processes generates the corresponding sulfinate salts, which can be further derivatised to provide sulfonyl-containing boronate esters, such as sulfones and sulfonyl fluorides. [ABSTRACT FROM AUTHOR]

Fluorine, as the most electronegative element, can replace the oxygen ligands of functional groups under given conditions. These fluoride groups are more or less different from the pure oxide groups in composition, symmetry, polarizability, transmittancy, etc. The rational use of these differences is expected to improve the probability of noncentrosymmetric structures and the comprehensive performance of second-harmonic-generation (SHG) materials. In this feature article, we introduce the recent developments in fluoride selenite and tellurite SHG materials together with highlighting our contributions, including Se(IV) and Te(IV) compounds with (i) d0 transition metal oxyfluoride octahedron, (ii) IIIA metal oxyfluoride octahedron, (iii) fluoride lone pair cation polyhedron, and (iv) other fluoride polyhedron. The future perspectives of fluoride selenite and tellurite SHG materials are also discussed. [ABSTRACT FROM AUTHOR]

The production of 18F-labelled microbubbles (MBs) via the aluminium-[18F]fluoride ([18F]AlF) radiolabelling method and facile inverse-electron-demand Diels–Alder (IEDDA) 'click' chemistry is reported. An [18F]AlF-NODA-labelled tetrazine was synthesised in excellent radiochemical yield (>95% RCY) and efficiently conjugated to a trans-cyclooctene (TCO) functionalised phospholipid (40–50% RCY), which was incorporated into MBs (40–50% RCY). To demonstrate the potential of producing 18F-labelled MBs for clinical studies, we also describe a kit-based approach which is amenable for use in a hospital radiopharmacy setting. [ABSTRACT FROM AUTHOR]

We demonstrate an economical polytetrafluoroethylene-assisted fluorination method to synthesize three binary sodium-rich fluorides Na2MVF7 (M = Mn, Fe, and Co). The optimal Na2FeVF7 cathode delivers a high reversible capacity of 146.5 mA h g−1 based on active Fe2+/Fe3+ and V3+/V4+ redox reactions in sodium-ion batteries. A steady cycling performance with a high capacity retention of 95% over 200 cycles is achieved owing to the negligible structural change during Na+ insertion/extraction. [ABSTRACT FROM AUTHOR]

Self-assembly and characterisation of a supramolecular trigonal bipyramidal iron cage containing an [FeIII(μ2-F)6(FeII)3]3+ star motif at its core is reported. The complex can be formed in a one step reaction using an heterotopic ligand that supports site-specific incorporation of iron in three distinct electronic configurations: low-spin FeII, high-spin FeII and high-spin FeIII, with iron(II) tetrafluoroborate as the source of the bridging fluorides. Formation of a μ2-F bridged mixed-valence FeII–FeIII star is unprecedented. The peripheral high-spin FeII centres of the mixed-valence tetranuclear star incorporated in the iron cage are highly anisotropic and engage in F-mediated antiferromagnetic exchange with the central FeIII ion. [ABSTRACT FROM AUTHOR]

Fluoride is a promising charge carrier for batteries due to its high charge/mass ratio and small radius. Here, we report commercial copper powder exhibits a reversible capacity of up to 222 mA h g−1 in a saturated electrolyte of 16 m KF. This electrolyte suppresses dissolution of CuF2, the charged product. Furthermore, the KF solid comprised in the Cu electrode facilitates a high initial capacity. Our results showcase the potential of aqueous fluoride batteries using copper as an electrode. [ABSTRACT FROM AUTHOR]

Aryl fluorosulfonates are developed as a deoxyfluorinating reagent in the transformation of primary and secondary alcohols into the corresponding alkyl fluorides. These reagents feature easy availability, low-cost, high stability and high efficiency. Diverse functionalities including aldehyde, ketone, ester, halogen, nitro, alkene, and alkyne are well tolerated under mild reaction conditions. [ABSTRACT FROM AUTHOR]

Conversion-type NiCoMn triple perovskite fluorides (KNCMF-622) have been explored for advanced aqueous supercapacitors (ASCs), batteries (ABs) and supercapatteries (i.e., ASC/Bs). The ASC/Bs outperform the ASCs and ABs, owing to the synergistic effect of capacitive, pseudocapacitive and faradaic characteristics, showing great significance in developing energy storage devices. [ABSTRACT FROM AUTHOR]

A F-deficient and high-Mn ternary perovskite fluoride anode (K1.00Ni0.06Co0.14Mn0.80F2.92, KNCMF-3#) has been explored for advanced Li-ion batteries (LIBs), showing a dominant conversion mechanism. Notably, the KNCMF-3#//LiFePO4 (LFP) LIBs furnish an ultra-high performance of 270.5–35.9 W h kg−1/0.63–11.6 kW kg−1/71% retention/5000 cycles/5 A g−1. [ABSTRACT FROM AUTHOR]

A highly chemoselective reductive deuteration of acyl fluorides to provide α,α-dideuterio alcohols with exquisite levels of deuterium incorporation was developed using SmI2 and D2O as the deuterium source. This method introduces acyl fluorides as attractive radical precursors for the generation of reactive acyl-type fluoride ketyls that should find widespread application in many synthetic strategies involving single electron transfer processes. [ABSTRACT FROM AUTHOR]

The reactivity of NOBF4 towards silylene, disilene, germylene, stannylenes has been described. Smooth syntheses of compounds of composition [PhC(NtBu)2E(= O → BF3)N(SiMe3)2, E = Si (3) and Ge (4)] were accomplished from the corresponding tetrylenes. An unusual heterocycle (10) featuring B, Sn, N, P, and O atoms was obtained from the reaction with a stannylene, while a 1,2-vicinal anti addition of fluoride was observed with a disilene (12). [ABSTRACT FROM AUTHOR]

We present the synthesis and characterization of the first non-classical Cl(I) polyinterhalide [NMe4][F(ClF)3] as well as the homologous polychloride [NPr3Me][Cl7]. Both salts were obtained from the reaction of the corresponding ammonium chlorides with ClF or Cl2, respectively. Quantum-chemical investigations predict an unexpected planar structure for the [F(ClF)3]− anion. [ABSTRACT FROM AUTHOR]

We present the synthesis and characterization of the first non-classical Cl(I) polyinterhalide [NMe4][F(ClF)3] as well as the homologous polychloride [NPr3Me][Cl7]. Both salts were obtained from the reaction of the corresponding ammonium chlorides with ClF or Cl2, respectively. Quantum-chemical investigations predict an unexpected planar structure for the [F(ClF)3]− anion. [ABSTRACT FROM AUTHOR]

We report a general palladium-catalyzed one-pot procedure for the synthesis of phosphonates, phosphinates and phosphine oxides from phenols mediated by sulfuryl fluoride. It features mild conditions, broad substrate scope, high functionality tolerance and water insensitivity. The utility of this procedure has been well demonstrated by gram-scale synthesis, sequential synthesis of click chemistry building blocks, late-stage decoration of drugs and natural products and on-DNA synthesis of phosphine oxide for a DNA-encoded library (DEL). [ABSTRACT FROM AUTHOR]

One new combination, alkali-metal and alkaline earth-metal selenite fluoride, LiBa3Bi6(SeO3)7F11 (LBBSF) and its analogue Ba3Bi6.5(SeO3)7F10.5O0.5 (BBSF) were reported here for the first time. Unusual aliovalent cation substitution between them affected the layer thickness and made the bond strains of [SeO3] enhanced, thereby inducing greater distortions and affecting the SHG efficiencies. This work may provide thoughts for exploring new NLO materials. [ABSTRACT FROM AUTHOR]

One new combination, alkali-metal and alkaline earth-metal selenite fluoride, LiBa3Bi6(SeO3)7F11 (LBBSF) and its analogue Ba3Bi6.5(SeO3)7F10.5O0.5 (BBSF) were reported here for the first time. Unusual aliovalent cation substitution between them affected the layer thickness and made the bond strains of [SeO3] enhanced, thereby inducing greater distortions and affecting the SHG efficiencies. This work may provide thoughts for exploring new NLO materials. [ABSTRACT FROM AUTHOR]

Ratiometric Raman spectroscopy represents a novel sensing approach for the detection of fluoride anions based on alkyne desilylation chemistry. This method enables rapid, anion selective and highly sensitive detection of fluoride in a simple paper-based assay format using a portable Raman spectrometer. [ABSTRACT FROM AUTHOR]

The effect of fluoride coatings, an effective approach to suppress HF corrosion, on the cycling stability of NCM523 cathodes is systematically studied. It is the first study to reveal that fluoride coatings significantly restrain interfacial reactions when, simultaneously, the fluoride suspension possesses an appropriate pH (near 4.0) and there is a small cation ionic radius. [ABSTRACT FROM AUTHOR]

The Cu2+-based breathing kagomé material Pb(OF)Cu3(SeO3)2(NO3) with both corner-sharing and edge-sharing has been synthesized. Magnetic measurements suggest ferromagnetic interactions inside the layers and antiferromagnetic interactions between the neighboring layers, leading to an antiferromagnetic ground state with a field-induced spin–flip transition at low temperature. [ABSTRACT FROM AUTHOR]

The fluoride anion-initiated reaction of phenyl aromatic carboxylates with (trifluoromethyl)trimethylsilane (Me3SiCF3) that results in the formation of O-silyl-protected 2-aryl-1,1,1,3,3,3-hexafluoroisopropanols is reported. A phenoxide anion, generated during the trifluoromethylation of the phenyl carboxylate, also activates the Me3SiCF3, which permits a catalytic amount of the fluoride anion source to be used. Various functional groups, which can be used for further elaboration, are tolerated in the reaction. [ABSTRACT FROM AUTHOR]

We report here that a fluorescent benzobisimidazolium salt (TBBI) can be used for the fluorescent and colorimetric detection of carbonyl sulfide (COS) over related heterocumulenes including CO2 and CS2 in wet MeCN. The reaction between TBBI and COS in the presence of fluoride yields a highly fluorescent (λem = 354 nm) and colored product (λmax = 321, 621 nm), that is readily observed by the naked eye. We view these results as a first step toward developing activity-based probes for COS detection. [ABSTRACT FROM AUTHOR]

We report here that energy migration during luminescence can be extremely minimized by caging the fluorescent centers in a molecular cluster of [Tb6(μ3-F)8(piv)10(Hpiv)4DMF]·xDMF·yH2O 1. Experimental and theoretical simulations reveal that bonding terbium with fluoride is the key to reducing the non-radiative multi-phonon relaxation processes, which is disparate to the common hydroxy-based lanthanide clusters. [ABSTRACT FROM AUTHOR]

Recent advances in the investigation of cobalt fluorides in organofluorine chemistry are highlighted. The preparation and reactivity of inorganic and organometallic cobalt fluorides are discussed. The in-depth understanding of the structures and reactivity of cobalt fluorides allows chemists to develop diverse innovative catalytic fluorination and C–F functionalization. [ABSTRACT FROM AUTHOR]

A versatile selectively addressable SuFEx click chemistry hub, but-3-ene-1,3-disulfonyl difluoride (BDF) was designed and synthesized through head-to-tail dimerization of ethenesulfonyl fluoride (ESF). BDF possesses three active sites to selectively participate in the construction of 4-membered, 5-membered and 6-membered cyclic sulfonamide (sultams) bearing aliphatic sulfonyl fluoride moieties for further manipulations in a fast, efficient and practical manner. [ABSTRACT FROM AUTHOR]

A fluoride stabilized sulfur-substituted uranyl complex [U(O)(S)F2] was prepared for the first time via oxidation of U(0) by SOF2 in cryogenic matrixes. The electron withdrawing character of F in this neutral complex does not cause the oxidation of the sulfido ligand by U(VI), but increases the strength and covalency of the U–O and U–S bonds. [ABSTRACT FROM AUTHOR]

A fluoride stabilized sulfur-substituted uranyl complex [U(O)(S)F2] was prepared for the first time via oxidation of U(0) by SOF2 in cryogenic matrixes. The electron withdrawing character of F in this neutral complex does not cause the oxidation of the sulfido ligand by U(VI), but increases the strength and covalency of the U–O and U–S bonds. [ABSTRACT FROM AUTHOR]

The first enantioselective phosphonyldifluoromethylation is enabled by the use of diethyl (difluoro(trimethylsilyl)-methyl)phosphonate reagent as a latent pronucleophile in the Lewis base catalyzed substitution of allylic fluorides. The reaction proceeds as a kinetic resolution to produce both the difluoromethylphosphonate products and the remaining fluorides in good yields and with high stereoselectivity. The use of cinchona based alkaloid catalysts enables the facile synthesis of both enantiomers of the difluoromethylphosphonate products. [ABSTRACT FROM AUTHOR]

Calix[3]pyrroles were synthesized for the first time. These macrocycles display versatile guest binding ability based on the bridges connecting the two α-positions of the tripyrrane moiety e.g. with an ethene bridge they showed colorimetric sensing of fluoride and cyanide ions, whereas with a phenylene spacer they exhibited fluorometric sensing of fluoride ions only, and the macrocycle with an ethylene unit acted as a host towards the water molecule with unique penta-coordinated oxygen in the solid state. [ABSTRACT FROM AUTHOR]