Pub Date : 2026-07-01Epub Date: 2026-06-16DOI: 10.1016/j.jfluchem.2026.110589
Raphaël Pronovost, Raphaël Gauthier, Nikolaos V. Tzouras, Steven P. Nolan, Jean-François Paquin
The gold-catalyzed addition of phenols, alcohols, and carboxylic acids to 2,2,2-trifluoroethyl-substituted alkynes is reported. The reaction is highly regioselective, once again illustrating the strong directing effect of the trifluoromethyl group in gold-catalyzed additions to alkynes through its inductive influence.
{"title":"Regioselective gold-catalyzed addition of phenols, alcohols and carboxylic acids to 2,2,2-trifluoroethyl-substituted alkynes","authors":"Raphaël Pronovost, Raphaël Gauthier, Nikolaos V. Tzouras, Steven P. Nolan, Jean-François Paquin","doi":"10.1016/j.jfluchem.2026.110589","DOIUrl":"10.1016/j.jfluchem.2026.110589","url":null,"abstract":"<div><div>The gold-catalyzed addition of phenols, alcohols, and carboxylic acids to 2,2,2-trifluoroethyl-substituted alkynes is reported. The reaction is highly regioselective, once again illustrating the strong directing effect of the trifluoromethyl group in gold-catalyzed additions to alkynes through its inductive influence.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"292 ","pages":"Article 110589"},"PeriodicalIF":1.6,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148565658","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-01Epub Date: 2026-06-25DOI: 10.1016/j.jfluchem.2026.110593
Yujie Yan, Tao Huang, Chengrong Wang, Liqiong Luo, Rufang Peng, Bo Jin
Four fluorinated cast-carrier explosives were prepared using fluorinated benzene rings as raw materials via a high-temperature nitration method: 2,4-difluoro-3-methyl-1,5-dinitrobenzene (mDFDNT), 3-Fluoro-2-methyl-4,6-dinitroaniline (mDFDNTN), 1,2-difluoro-4-methyl-3,5-dinitrobenzene (qDFDNT), and 6-fluoro-3-methyl-2,4-dinitroaniline (qDFDNTN). The densities of the four explosives were 1.86, 1.681, 1.680, and 1.683 g cm−1, respectively, with melting points of 79.6 °C, 182.3 °C, 52.7 °C, and 129.3 °C, respectively. They exhibited moderate mechanical sensitivity, among them, mDFDNT, mDFDNTN and qDFDNT possess an impact sensitivity (IS) ≥ 35 J and friction sensitivity (FS) ≥ 360 N, while qDFDNTN shows IS ≥ 30 J and FS ≥ 324 N. The enthalpy of formation was calculated using the Gaussian 09 program at the CBS-4M level and obtained through an atomization reaction scheme. The heats of formation were -342.09 kJ/mol, -191.44 kJ/mol, -334.11 kJ/mol, and -181.07 kJ/mol, respectively; the detonation velocities were 7017, 6833, 7035, and 6791 m/s, respectively; and the corresponding detonation pressures were 21.4, 20.2, 21.5, and 19.8 GPa. mDFDNTN had the highest melting point due to the enhanced intermolecular hydrogen bonding caused by the introduction of amino groups; Hirshfeld surface analysis also confirmed this conclusion. Though mDFDNT/qDFDNT and mDFDNTN/qDFDNTN have the same molecular formula, their substituents are located at different positions, and differing only in the position of the substituents, the four compounds exhibited significant differences in melting points, indicating that the position and type of substituents have a crucial influence on the melting point of cast-supported explosives.
{"title":"Influences of substituent position and type on the melting point of fluorinated cast carrier explosives","authors":"Yujie Yan, Tao Huang, Chengrong Wang, Liqiong Luo, Rufang Peng, Bo Jin","doi":"10.1016/j.jfluchem.2026.110593","DOIUrl":"10.1016/j.jfluchem.2026.110593","url":null,"abstract":"<div><div>Four fluorinated cast-carrier explosives were prepared using fluorinated benzene rings as raw materials via a high-temperature nitration method: 2,4-difluoro-3-methyl-1,5-dinitrobenzene (mDFDNT), 3-Fluoro-2-methyl-4,6-dinitroaniline (mDFDNTN), 1,2-difluoro-4-methyl-3,5-dinitrobenzene (qDFDNT), and 6-fluoro-3-methyl-2,4-dinitroaniline (qDFDNTN). The densities of the four explosives were 1.86, 1.681, 1.680, and 1.683 g cm<sup>−1</sup>, respectively, with melting points of 79.6 °C, 182.3 °C, 52.7 °C, and 129.3 °C, respectively. They exhibited moderate mechanical sensitivity, among them, mDFDNT, mDFDNTN and qDFDNT possess an impact sensitivity (<em>IS</em>) ≥ 35 J and friction sensitivity (<em>FS</em>) ≥ 360 N, while qDFDNTN shows <em>IS</em> ≥ 30 J and <em>FS</em> ≥ 324 N. The enthalpy of formation was calculated using the Gaussian 09 program at the CBS-4M level and obtained through an atomization reaction scheme. The heats of formation were -342.09 kJ/mol, -191.44 kJ/mol, -334.11 kJ/mol, and -181.07 kJ/mol, respectively; the detonation velocities were 7017, 6833, 7035, and 6791 m/s, respectively; and the corresponding detonation pressures were 21.4, 20.2, 21.5, and 19.8 GPa. mDFDNTN had the highest melting point due to the enhanced intermolecular hydrogen bonding caused by the introduction of amino groups; Hirshfeld surface analysis also confirmed this conclusion. Though mDFDNT/qDFDNT and mDFDNTN/qDFDNTN have the same molecular formula, their substituents are located at different positions, and differing only in the position of the substituents, the four compounds exhibited significant differences in melting points, indicating that the position and type of substituents have a crucial influence on the melting point of cast-supported explosives.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"292 ","pages":"Article 110593"},"PeriodicalIF":1.6,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148587711","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-01Epub Date: 2026-07-02DOI: 10.1016/j.jfluchem.2026.110594
Ishika Jaitly, Henry Parkins, Oscar Stokoe, Olivia A. Clink, Nicholas W. Barnes, Simona S. Capomolla, Mariah R. Stavrou, Celine Valant, Nicola J. Smith, Luke Hunter
Imipramine is a tricyclic antidepressant (TCA) that inhibits the serotonin reuptake transporter (SERT). However, the clinical use of TCAs such as imipramine is limited by side-effects arising from antagonism of several off-target receptors. In this work, stereospecific fluorination is investigated as a strategy for enhancing the potency and selectivity of imipramine through conformational bias. In contrast to prediction, fluorination of imipramine is found to confer reduced potency and selectivity towards SERT, and this may be attributable to clashes between fluorine and hydroxyl‑bearing amino acid residues within the SERT binding site.
{"title":"Investigating the effect of stereospecific fluorination on the potency and selectivity of the tricyclic antidepressant, imipramine","authors":"Ishika Jaitly, Henry Parkins, Oscar Stokoe, Olivia A. Clink, Nicholas W. Barnes, Simona S. Capomolla, Mariah R. Stavrou, Celine Valant, Nicola J. Smith, Luke Hunter","doi":"10.1016/j.jfluchem.2026.110594","DOIUrl":"10.1016/j.jfluchem.2026.110594","url":null,"abstract":"<div><div>Imipramine is a tricyclic antidepressant (TCA) that inhibits the serotonin reuptake transporter (SERT). However, the clinical use of TCAs such as imipramine is limited by side-effects arising from antagonism of several off-target receptors. In this work, stereospecific fluorination is investigated as a strategy for enhancing the potency and selectivity of imipramine through conformational bias. In contrast to prediction, fluorination of imipramine is found to confer reduced potency and selectivity towards SERT, and this may be attributable to clashes between fluorine and hydroxyl‑bearing amino acid residues within the SERT binding site.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"292 ","pages":"Article 110594"},"PeriodicalIF":1.6,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148587713","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We report the synthesis and reactivity of a novel bis(hypervalent iodine) reagent incorporating a perfluoroalkylene chain. This reagent was readily synthesized in two steps from commercially available α,ω-dibromoperfluoroalkanes, and fully characterized by NMR spectroscopy and high-resolution mass spectrometry. Furthermore, we demonstrated that the reagent reacts with various alkenes and nucleophiles in the presence of a copper(I) catalyst, enabling efficient three-component transformations at both termini of the perfluoroalkylene chain under mild conditions. This methodology provides a new and efficient strategy for incorporating of perfluoroalkylene chains into organic molecules.
{"title":"Synthesis and reactions of perfluoroalkylene-bridged bis(hypervalent iodine) reagents","authors":"Toshihiko Heima, Kaishi Ogami, Motohiro Yasui, Shigeyuki Yamada, Tsutomu Konno","doi":"10.1016/j.jfluchem.2026.110599","DOIUrl":"10.1016/j.jfluchem.2026.110599","url":null,"abstract":"<div><div>We report the synthesis and reactivity of a novel bis(hypervalent iodine) reagent incorporating a perfluoroalkylene chain. This reagent was readily synthesized in two steps from commercially available α,ω-dibromoperfluoroalkanes, and fully characterized by NMR spectroscopy and high-resolution mass spectrometry. Furthermore, we demonstrated that the reagent reacts with various alkenes and nucleophiles in the presence of a copper(I) catalyst, enabling efficient three-component transformations at both termini of the perfluoroalkylene chain under mild conditions. This methodology provides a new and efficient strategy for incorporating of perfluoroalkylene chains into organic molecules.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"292 ","pages":"Article 110599"},"PeriodicalIF":1.6,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148582298","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-01Epub Date: 2026-07-12DOI: 10.1016/j.jfluchem.2026.110600
Biao Zhou, Xikang Zhang, Xingjian Kang, Muying Ge, Yang Guo, Kai Wang, Hideki Yoshioka
Hydrofluoroether (HFE-7200) is a highly promising working fluid for immersion liquid cooling due to its excellent environmental profile, superior insulation properties, and phase-change heat transfer performance. However, it is susceptible to thermal decomposition under high-temperature conditions. To investigate its high-temperature decomposition behavior, pyrolysis experiments were performed in a tube furnace, and the resulting products under various conditions were analyzed via gas chromatography-mass spectrometry (GC–MS). Additionally, the reaction pathways were explored using Gaussian software based on Density Functional Theory (DFT). The results demonstrate that HFE-7200 initiates primary cracking at 400 °C, the 500–700 °C range serves as a rapid growth interval for the pyrolysis conversion, and deep pyrolysis is observed above 700 °C. At 800 °C, near-complete decomposition is achieved within 2 s. The major organic products identified include C2H4, CF3CF=CF2, (CF3)2CCF2, (CF3)2C–C(CF3)2, and CF3OCH2CH3. Furthermore, the HF yield increases significantly with temperature. Four primary reaction pathways were constructed: Pathway A originates from C–O bond cleavage, Pathway B involves C–C bond homolysis, Pathway C is characterized by radical chain reactions, and Pathway D generates ethylene via β-H elimination. This study provides valuable insights and a reference for assessing the decomposition risks of HFE-7200 in high-temperature applications.
{"title":"Investigation on the temperature dependence of decomposition reaction mechanism of C4F9OC2H5","authors":"Biao Zhou, Xikang Zhang, Xingjian Kang, Muying Ge, Yang Guo, Kai Wang, Hideki Yoshioka","doi":"10.1016/j.jfluchem.2026.110600","DOIUrl":"10.1016/j.jfluchem.2026.110600","url":null,"abstract":"<div><div>Hydrofluoroether (HFE-7200) is a highly promising working fluid for immersion liquid cooling due to its excellent environmental profile, superior insulation properties, and phase-change heat transfer performance. However, it is susceptible to thermal decomposition under high-temperature conditions. To investigate its high-temperature decomposition behavior, pyrolysis experiments were performed in a tube furnace, and the resulting products under various conditions were analyzed via gas chromatography-mass spectrometry (GC–MS). Additionally, the reaction pathways were explored using Gaussian software based on Density Functional Theory (DFT). The results demonstrate that HFE-7200 initiates primary cracking at 400 °C, the 500–700 °C range serves as a rapid growth interval for the pyrolysis conversion, and deep pyrolysis is observed above 700 °C. At 800 °C, near-complete decomposition is achieved within 2 s. The major organic products identified include C<sub>2</sub>H<sub>4</sub>, CF<sub>3</sub>CF=CF<sub>2</sub>, (CF<sub>3</sub>)<sub>2</sub>C<img>CF<sub>2</sub>, (CF<sub>3</sub>)<sub>2</sub>C–C(CF<sub>3</sub>)<sub>2</sub>, and CF<sub>3</sub>OCH<sub>2</sub>CH<sub>3</sub>. Furthermore, the HF yield increases significantly with temperature. Four primary reaction pathways were constructed: Pathway A originates from C–O bond cleavage, Pathway B involves C–C bond homolysis, Pathway C is characterized by radical chain reactions, and Pathway D generates ethylene via β-H elimination. This study provides valuable insights and a reference for assessing the decomposition risks of HFE-7200 in high-temperature applications.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"292 ","pages":"Article 110600"},"PeriodicalIF":1.6,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148582299","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-01Epub Date: 2026-07-02DOI: 10.1016/j.jfluchem.2026.110595
Michael C. Davis, Rebecca J. Dooley, Alexander A. Marchione
A tetrafluoroethylene-co-ethyl(vinyl)ether copolymer has been interrogated to evaluate polymer composition and probe incorporation of a triisopropoxyvinylsilane. Fluoropolymers have applications in the electronics and semiconductor industries but since fluorinated polymers have both hydro- and oleophobic properties adhesion to certain substrates can be a challenge. Modifiers, including silanes, can be incorporated to enhance substrate binding and provide a mechanism for crosslinking allowing the polymer to maintain a rigid network with a required geometry. The concentration and structure of silane in the uncrosslinked polymer are, therefore, critical for understanding physical performance. Nuclear Magnetic Resonance (NMR) allows polymer structure to be interrogated probing the unique electrochemical bonding environment of a nucleus of interest. Short range order can be elucidated by different multidimensional NMR experiments that probe connectivity either through space or through bond. In this study NMR has been utilized to characterize a polyfluorinated silane modifying polymer, where multiple nonequivalent silane structures are observed.
{"title":"Interrogation of silane incorporation in a modified tetrafluoroethylene-co-Ethyl(vinyl)ether fluoropolymer by nuclear magnetic resonance spectroscopy","authors":"Michael C. Davis, Rebecca J. Dooley, Alexander A. Marchione","doi":"10.1016/j.jfluchem.2026.110595","DOIUrl":"10.1016/j.jfluchem.2026.110595","url":null,"abstract":"<div><div>A tetrafluoroethylene-co-ethyl(vinyl)ether copolymer has been interrogated to evaluate polymer composition and probe incorporation of a triisopropoxyvinylsilane. Fluoropolymers have applications in the electronics and semiconductor industries but since fluorinated polymers have both hydro- and oleophobic properties adhesion to certain substrates can be a challenge. Modifiers, including silanes, can be incorporated to enhance substrate binding and provide a mechanism for crosslinking allowing the polymer to maintain a rigid network with a required geometry. The concentration and structure of silane in the uncrosslinked polymer are, therefore, critical for understanding physical performance. Nuclear Magnetic Resonance (NMR) allows polymer structure to be interrogated probing the unique electrochemical bonding environment of a nucleus of interest. Short range order can be elucidated by different multidimensional NMR experiments that probe connectivity either through space or through bond. In this study NMR has been utilized to characterize a polyfluorinated silane modifying polymer, where multiple nonequivalent silane structures are observed.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"292 ","pages":"Article 110595"},"PeriodicalIF":1.6,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148582301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-01Epub Date: 2026-07-04DOI: 10.1016/j.jfluchem.2026.110596
Yining Li, Qilong Shen
A ring-opening three-component reaction of carboxylic acid, a cyclic (thio)ether and a difluorocarbene precursor Ylide-CF2H was reported, affording difluoromethyl(thio)ethers in good yields. The reaction proceeds under simple and mild conditions, with good substrate compatibility. Although the mechanism remains speculative, a proposed pathway involves the initial activation of the Ylide-CF2H species through protonation of the malonate moiety, leading to the generation of difluorocarbene. Nucleophilic attack of difluorocarbene by the cyclic (thio)ether forms an oxonium ylide or sulfonium ylide, which undergoes protonation followed by nucleophilic attack of the α-carbon of the intermediate to afford the difluoromethyl(thio)ethers. Additionally, by switching the solvent to toluene, a direct difluoromethylation of carboxylic acids was observed, which provides an alternative transformation under modified conditions.
{"title":"Ylide-CF2H as difluorocarbene precursor for ring-opening difluoromethylation of cyclic (thio)ethers","authors":"Yining Li, Qilong Shen","doi":"10.1016/j.jfluchem.2026.110596","DOIUrl":"10.1016/j.jfluchem.2026.110596","url":null,"abstract":"<div><div>A ring-opening three-component reaction of carboxylic acid, a cyclic (thio)ether and a difluorocarbene precursor <strong>Ylide</strong>-<strong>CF<sub>2</sub>H</strong> was reported, affording difluoromethyl(thio)ethers in good yields. The reaction proceeds under simple and mild conditions, with good substrate compatibility. Although the mechanism remains speculative, a proposed pathway involves the initial activation of the <strong>Ylide</strong>-<strong>CF<sub>2</sub>H</strong> species through protonation of the malonate moiety, leading to the generation of difluorocarbene. Nucleophilic attack of difluorocarbene by the cyclic (thio)ether forms an oxonium ylide or sulfonium ylide, which undergoes protonation followed by nucleophilic attack of the α-carbon of the intermediate to afford the difluoromethyl(thio)ethers. Additionally, by switching the solvent to toluene, a direct difluoromethylation of carboxylic acids was observed, which provides an alternative transformation under modified conditions.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"292 ","pages":"Article 110596"},"PeriodicalIF":1.6,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148582302","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-01Epub Date: 2026-07-09DOI: 10.1016/j.jfluchem.2026.110598
Stefano Todisco, Paolo Antonio Di Lorenzo, Giacomo Saielli, Vito Gallo, Valeria Veronico, Salvatore Sgrò, Piero Mastrorilli
The perfluorinated ketone perfluoro-2-methyl-3-pentanone (1) is a fire protection fluid of great merchandise importance whose analysis of purity can be easily carried out by NMR techniques. However, while 1 is very stable (at least one year) in the neat state, it reacts with moisture when dissolved in NMR solvents such as acetone-d6, acetonitrile-d3 or dimethylsulfoxide-d6 producing the gem‑diol perfluoro-2-methyl-3,3-pentandiol (2) as the major product in acetone-d6 or in acetonitrile-d3; and a perfluoropropionic acid/CF3CFHCF3 (3/4) mixture in dimethylsulfoxide-d6. Good stability was observed in CDCl3 or in C6D6. A multinuclear NMR analysis using both a low-field machine (80 MHz benchtop spectrometer) and a medium-field machine (400 MHz spectrometer) and a DFT study that confirmed the existence of through-space spin-spin coupling for 1, as well as the mechanism of water induced degradation of 1, is reported.
{"title":"Degradation pathways of perfluoro-2-methyl-3-pentanone in different solvents: a multinuclear NMR and DFT study","authors":"Stefano Todisco, Paolo Antonio Di Lorenzo, Giacomo Saielli, Vito Gallo, Valeria Veronico, Salvatore Sgrò, Piero Mastrorilli","doi":"10.1016/j.jfluchem.2026.110598","DOIUrl":"10.1016/j.jfluchem.2026.110598","url":null,"abstract":"<div><div>The perfluorinated ketone perfluoro-2-methyl-3-pentanone (<strong>1</strong>) is a fire protection fluid of great merchandise importance whose analysis of purity can be easily carried out by NMR techniques. However, while <strong>1</strong> is very stable (at least one year) in the neat state, it reacts with moisture when dissolved in NMR solvents such as acetone-<em>d</em><sub>6</sub>, acetonitrile-<em>d</em><sub>3</sub> or dimethylsulfoxide-<em>d</em><sub>6</sub> producing the gem‑diol perfluoro-2-methyl-3,3-pentandiol (<strong>2</strong>) as the major product in acetone-<em>d</em><sub>6</sub> or in acetonitrile-<em>d</em><sub>3</sub>; and a perfluoropropionic acid/CF<sub>3</sub>CFHCF<sub>3</sub> (<strong>3</strong>/<strong>4</strong>) mixture in dimethylsulfoxide-<em>d</em><sub>6</sub>. Good stability was observed in CDCl<sub>3</sub> or in C<sub>6</sub>D<sub>6</sub>. A multinuclear NMR analysis using both a low-field machine (80 MHz benchtop spectrometer) and a medium-field machine (400 MHz spectrometer) and a DFT study that confirmed the existence of through-space spin-spin coupling for <strong>1</strong>, as well as the mechanism of water induced degradation of <strong>1</strong>, is reported.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"292 ","pages":"Article 110598"},"PeriodicalIF":1.6,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148582300","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-01Epub Date: 2026-07-07DOI: 10.1016/j.jfluchem.2026.110597
Katarzyna Kuder, Wojciech Grochala
This work explores the thermodynamic stability, crystal structures and magnetic properties of ternary Li–Ag(II)–F compounds. Convex-hull analysis shows all predicted structures slightly above the LiF + AgF2 decomposition line, indicating their metastability. Nevertheless, synthetic routes employing F2 gas or F radicals, or a thermal decomposition of LiAgF4 precursor, should allow for their preparation. All structures exhibit antiferromagnetic ground states, with LiAgF3_2 polymorph exhibiting an exceptionally large superexchange constant of ca. –380 meV within [Ag2F7] dimers.
{"title":"Theoretical prediction of novel Li–Ag(II)–F quantum magnets using evolutionary algorithms","authors":"Katarzyna Kuder, Wojciech Grochala","doi":"10.1016/j.jfluchem.2026.110597","DOIUrl":"10.1016/j.jfluchem.2026.110597","url":null,"abstract":"<div><div>This work explores the thermodynamic stability, crystal structures and magnetic properties of ternary Li–Ag(II)–F compounds. Convex-hull analysis shows all predicted structures slightly above the LiF + AgF<sub>2</sub> decomposition line, indicating their metastability. Nevertheless, synthetic routes employing F<sub>2</sub> gas or F radicals, or a thermal decomposition of LiAgF<sub>4</sub> precursor, should allow for their preparation. All structures exhibit antiferromagnetic ground states, with LiAgF<sub>3</sub>_2 polymorph exhibiting an exceptionally large superexchange constant of ca. –380 meV within [Ag<sub>2</sub>F<sub>7</sub>] dimers.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"292 ","pages":"Article 110597"},"PeriodicalIF":1.6,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148582297","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polyfluorinated chalcones react with hydroxylamine hydrochloride to form oximes, 3-hydroxylaminooximes, dihydroquinoline and benzisoxazole derivatives, depending on the chalcone structure and the reaction conditions. The last two structure types are formed as a result of intramolecular cyclization by replacing the ortho-fluorine atom in the perfluoro phenyl ring next to the carbonyl group.
{"title":"Reactions of polyfluorinated chalcones with hydroxylamine and subsequent intramolecular cyclization","authors":"I.N. Gavrilov, N.A. Orlova, P.A. Demakov, T.V. Rybalova","doi":"10.1016/j.jfluchem.2026.110591","DOIUrl":"10.1016/j.jfluchem.2026.110591","url":null,"abstract":"<div><div>Polyfluorinated chalcones react with hydroxylamine hydrochloride to form oximes, 3-hydroxylaminooximes, dihydroquinoline and benzisoxazole derivatives, depending on the chalcone structure and the reaction conditions. The last two structure types are formed as a result of intramolecular cyclization by replacing the ortho-fluorine atom in the perfluoro phenyl ring next to the carbonyl group.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"292 ","pages":"Article 110591"},"PeriodicalIF":1.6,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148587712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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