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Recent Advances on Fluorine Chemistry

A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Physical Chemistry and Chemical Physics".

Deadline for manuscript submissions: 31 December 2024 | Viewed by 5040

Special Issue Editor

Dr. Mikhail Moskalik

E-Mail Website
Guest Editor
AE Favorsky Irkutsk Institute of Chemistry, Siberian Division of the Russian Academy of Sciences, 1 Favorsky Street, 664033 Irkutsk, Russia
Interests: trifluoromethanesulfonamides; bis(trifluoromethanesulfonyl)imide; triflates; selective fluorination; oxidative reactions; amination
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Fluorine is a unique element due to its introduction as a substituent in various classes of chemical compounds. The uniqueness of fluorine lies in the special polarizing and steric properties of the fluorine atom, which surprisingly affects the chemical and physical properties of molecules. Such specific features affect all stages of work and research on fluorine-containing structures: unique methodologies for the synthesis and analysis of fluorine-containing compounds, the study of the biochemical mechanisms of the action of such compounds on living systems, the study of the synthesis and structure of new materials, etc. Among fluorine compounds, several general groups can be distinguished: complex and inorganic fluorine derivatives, as well as a wide class of organic fluorine-containing compounds. The latter, as a rule, are divided into weakly fluorinated (containing one or more isolated fluorine-containing substituents, for example, CH2F, CF2, CF3) and polyfluorinated (or perfluoro-) derivatives. Surprisingly, fluorine and many of its derivatives are extremely toxic substances for humans, but at the same time, fluorine is necessary for human health. Organic fluorine compounds are very rare in nature, only about three dozen such substances are known (for example, fluoroacetic acid, fluoroacetone, ω-fluorooleic acid). All these natural organofluorine compounds are extremely toxic. Despite the fact that natural fluorine-containing substances are very few in number, synthetic organofluorine derivatives are a very important objects of research, and the organic chemistry of fluorine is completely created by humans. Although elemental fluorine is toxic to all living things, fluorine-containing drugs are increasingly used in medical practice (about a third of all agrochemicals and pharmaceuticals produced contain at least one fluorine atom). Of the special sign drugs, examples such as Celebrex, Perftoran, Fluoxetine, Atorvastatin can be cited. The introduction of fluorine changes the physical, chemical, and biological properties of the initial compound due to conformational changes, changes in acid–base properties, and the ability to form hydrogen bonds, which play an important role in biological systems. Fluorine derivatives simultaneously have both high hydrophilicity and good lipophilicity, as well as high stability and chemical inertness to metabolic degradation, which makes it possible to reduce the dose of the drug. Thus, fluorine-containing compounds are important and interesting objects for research in the field of biochemistry, molecular chemistry, medicine, and pharmacy. To that end, this Special Issue of the International Journal of Molecular Sciences, Recent Advance on Fluorine Chemistry, will include original research papers and reviews on the latest developments in fluorine chemistry.

Dr. Mikhail Moskalik
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. International Journal of Molecular Sciences is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. There is an Article Processing Charge (APC) for publication in this open access journal. For details about the APC please see here. Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • fluorine
  • оrganofluorine compounds
  • fluorine-containing building blocks
  • fluorine introduction
  • defluorination
  • fluorocarbons
  • fluorine NMR
  • fluorine biocatalysis
  • trifluoromethyl
  • lipophilicity
  • fluorine drugs

Published Papers (6 papers)

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Research

18 pages, 3103 KiB  
Article
Optimization of Calcium Fluoride Crystallization Process for Treatment of High-Concentration Fluoride-Containing Semiconductor Industry Wastewater
by Arindam Sinharoy, Ga-Young Lee and Chong-Min Chung
Int. J. Mol. Sci. 2024, 25(7), 3960; https://doi.org/10.3390/ijms25073960 - 2 Apr 2024
Cited by 2 | Viewed by 782
Abstract
This study utilized a fluidized bed reactor (FBR) for fluoride removal from high-concentration fluoride-ion-containing simulated semiconductor industry wastewater and recovered high-purity CaF2 crystals. The effects of hydraulic retention time (HRT), pH, Ca2+ to F− ratio, upflow velocity, seed size and [...] Read more.
This study utilized a fluidized bed reactor (FBR) for fluoride removal from high-concentration fluoride-ion-containing simulated semiconductor industry wastewater and recovered high-purity CaF2 crystals. The effects of hydraulic retention time (HRT), pH, Ca2+ to F− ratio, upflow velocity, seed size and seed bed height were investigated by performing lab-scale batch experiments. Considering fluoride removal and CaF2 crystallization efficiency, 5 h HRT, pH 6, seed height of 50 cm and [Ca2+]/[F−] ratio of 0.55 (mol/mol) were found to be optimum. The effect of the interaction between the important process parameters on fluoride removal was further analyzed using response surface methodology (RSM) experimental design. The results showed that all the individual parameters have a significant impact (p = 0.0001) on fluoride removal. SEM-EDX and FTIR analysis showed the composition of the crystals formed inside FBR. HR-XRD analysis confirmed that the crystalline structure of samples was mainly CaF2. The results clearly demonstrated the feasibility of silica seed material containing FBR for efficient removal and recovery of fluoride as high-purity calcium fluoride crystals. Full article
(This article belongs to the Special Issue Recent Advances on Fluorine Chemistry)
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18 pages, 2339 KiB  
Article
Lanthanide Contraction in LnF3 (Ln = Ce-Lu) and Its Chemical and Structural Consequences: Part 2: Specialized Empirical System of R3+ (R = Y, La, and 14 Ln) and F1− Ionic Radii for RF3 Series
by Boris P. Sobolev and Elena A. Sulyanova
Int. J. Mol. Sci. 2023, 24(23), 17080; https://doi.org/10.3390/ijms242317080 - 3 Dec 2023
Viewed by 781
Abstract
A specialized empirical (Spec-zd Emp) system of ionic radii (SIR) for R = Y3+, La3+, Ln3+, and F1− (R rare earth elements (REE)) was derived from the dependence of [...] Read more.
A specialized empirical (Spec-zd Emp) system of ionic radii (SIR) for R = Y3+, La3+, Ln3+, and F1− (R rare earth elements (REE)) was derived from the dependence of lanthanide contraction (LC) on the atomic number (Z) of lanthanides (Ln). LC decreased the radius of the cation with increasing Z. The structures of t-RF3 (LaF3-NdF3, “pseudo t-SmF3”) of the LaF3 type, 11 β-LnF3 (Ln = Sm-Lu), and β-YF3 of the β-YF3 type were studied. The empirical basis of the shortest (F-F)min and (R-F)min distances was calculated from the structural data for the RF3 complete series. The dependence of (F-F)min on Z reached saturation at Z = 67 (Ho). The base F1− radius r− = 1.2539(16) Å was calculated as the arithmetic mean of five (F-F)min in LnF3 with Ln = Ho-Lu. For the LnF3 series with Ln contributions up to 75 % wt., the dependence of (Ln-F)min on Z reflected the non-uniformity of the 4f orbital filling. SIR was calculated as the difference in the empirical constants of RF3 (ionic radii of (R,Ln)3+ (r+) and F1− (r−)), the change in which was continuous over the series and did not depend on the type of structure: r+ = (ZR-F)min − ½(F-F)min (Z = 57–71). The changes in LC in the LnF3 series were described by a third-degree polynomial. LC reduced r+ by 24% (percentage relative to less) from 1.1671(16) Å (La3+) to 0.9439(17) Å (Lu3+). In the Spec-zd Emp SIR, r+ were constants that did not require corrections for a coordination number (CN). A comparison of r+ in the Spec-zd Emp SIR with other SIRs was performed. Full article
(This article belongs to the Special Issue Recent Advances on Fluorine Chemistry)
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12 pages, 2693 KiB  
Article
Lanthanide Contraction in LnF3 (Ln = Ce-Lu) and Its Chemical and Structural Consequences: Part 1: Location of YF3 in the LnF3 Series According to Its Chemical and Structural Characteristics
by Boris P. Sobolev and Elena A. Sulyanova
Int. J. Mol. Sci. 2023, 24(23), 17013; https://doi.org/10.3390/ijms242317013 - 30 Nov 2023
Cited by 1 | Viewed by 599
Abstract
A lanthanide contraction(LC) of 14 lanthanides (Ln) from 58Ce to 71Lu consists of the interaction of Ln nucleus with 4f-electrons. Rare earth elements (REEs—R) include Sc, Y, La, and 14 Ln. They are located [...] Read more.
A lanthanide contraction(LC) of 14 lanthanides (Ln) from 58Ce to 71Lu consists of the interaction of Ln nucleus with 4f-electrons. Rare earth elements (REEs—R) include Sc, Y, La, and 14 Ln. They are located in 4–6th periods of the subgroup of group III. The electronic structure divides R into short (d- Sc, Y, La) and long (14 f-elements Ce-Lu) homologous series. The most important chemical consequence of LC is the creation of a new conglomerate of 16 RF3 by mixing fluorides of d- (Y, La) and f-elements. This determines the location of YF3 among LnF3. The location of YF3 depends on the structural (formula volumes—Vform) and thermochemical (temperatures and heats of phase transformations, phase diagrams) properties. The location of YF3 between HoF3 and ErF3 was determined by Vform at a standard pressure (Pst) and temperature (Tst). The location of YF3 according to heats of phase transformations ΔHfus and ΔHtrans is in a dimorphic structural subgroup (SSGr) D (Ln = Er-Lu), but without the exact “pseudo ZY”. According to the temperatures of phase transformations (Ttrans) in LnF3 (Ln = Dy-Lu), YF3 is located in the SSGr D between ErF3 and TmF3. The ErF3-YF3 and YF3-TmF3 phase diagrams show it to be between ErF3 and TmF3. The crystals of five β-LnF3 (Ln = Ho-Lu) and β-YF3 were obtained in identical conditions and their crystal structures were studied. Vform (at Pst and Tst) with “pseudo” atomic number ZY = 67.42 was calculated from the unit cell parameters, which were defined with ±5 × 10−4 Å accuracy. It determines the location of YF3 between HoF3 and ErF3. Full article
(This article belongs to the Special Issue Recent Advances on Fluorine Chemistry)
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12 pages, 2080 KiB  
Article
The Reactions of Alkenes with Phenyl-N-triflylimino-λ3-iodane: Solvent and Oxidant Impact
by Mikhail Yu. Moskalik, Anton S. Ganin and Bagrat A. Shainyan
Int. J. Mol. Sci. 2023, 24(21), 15947; https://doi.org/10.3390/ijms242115947 - 3 Nov 2023
Viewed by 708
Abstract
The reactions of alkenes with phenyl-N-triflylimino-λ3-iodane PhI=NTf (1) have been studied in different conditions. In methylene chloride, in the presence of N-halosuccinimides, the products of mono and bis-triflamidation were obtained. In MeCN, the product of bromotriflamidation [...] Read more.
The reactions of alkenes with phenyl-N-triflylimino-λ3-iodane PhI=NTf (1) have been studied in different conditions. In methylene chloride, in the presence of N-halosuccinimides, the products of mono and bis-triflamidation were obtained. In MeCN, the product of bromotriflamidation (with NBS) with solvent interception or of bis-triflamidation (with NIS) is formed. The reaction with trans-stilbene in acetonitrile with NBS gave rise to cyclization to 2-methyl-4,5-diphenyl-1-triflyl-4,5-dihydro-1H-imidazole. In contrast, with NIS as an oxidant, both in CH2Cl2 and MeCN, the major product was 2,3-diphenyl-1-triflylaziridine formed in good yield. With NBS, aziridine is also formed but as a minor product, the major one being a mixture of diastereomers of the product of bromotriflamidation. The reaction of compound 1 with vinylcyclohexane in methylene chloride affords the mixtures of regioisomers of the products of halotriflamidation, whereas in acetonitrile, the products of solvent interception and cyclization to the imidazoline are formed. A mechanism explaining the formation of all isolated products is proposed. Full article
(This article belongs to the Special Issue Recent Advances on Fluorine Chemistry)
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13 pages, 2916 KiB  
Article
Thermodynamic Origin of Negative Thermal Expansion Based on a Phase Transition-Type Mechanism in the GdF3-TbF3 System
by Elena A. Sulyanova and Boris P. Sobolev
Int. J. Mol. Sci. 2023, 24(19), 14944; https://doi.org/10.3390/ijms241914944 - 6 Oct 2023
Cited by 1 | Viewed by 963
Abstract
Multicomponent fluorides of rare earth elements (REEs—R) are phase transition-type negative thermal expansion (NTE-II) materials. NTE-II occurs in RF3-R′F3 systems formed by “mother” single-component dimorphic RF3 (R = Pm, [...] Read more.
Multicomponent fluorides of rare earth elements (REEs—R) are phase transition-type negative thermal expansion (NTE-II) materials. NTE-II occurs in RF3-R′F3 systems formed by “mother” single-component dimorphic RF3 (R = Pm, Sm, Eu, and Gd) with a giant NTE-II. There are two structural types of RF3 polymorphic modifications: low-temperature β-YF3 (β−) and high-temperature LaF3 (t−). The change in a structural type is accompanied by a density anomaly: a volume of one formula unit (Vform) Vβ− >Vt−. The empirical signs of volumetric changes ΔV/V of NTE-II materials were considered. For the GdF3-TbF3 model system, an “operating-temperature window ΔT” and a two-phase composition of NTE-II materials follows from the thermodynamics of chemical systems: the phase rule and the principle of continuity. A necessary and sufficient sign of NTE-II is a combination of polymorphism and the density anomaly. Isomorphism in RF3-R′F3 systems modifies RF3 chemically by forming two-component t− and β− type R1−xR’xF3 solid solutions (ss). Between the two monovariant curves of ss decay, a two-phase area with ΔTtrans > 0 (the “window ΔT”) forms. A two-phase composite (t−ss + β−ss) is an NTE-II material. Its constituent t−ss and β−ss phases have different Vform corresponding to the selected T. According to the lever rule on a conode, Vform is calculated from the t−ss and β−ss compositions, which vary with T along two monovariant curves of ss decay. For the GdF3-TbF3 system, ΔV/V = f(T), ΔV/V = f(ΔT) and the “window ΔT” = f(x) dependencies were calculated. Full article
(This article belongs to the Special Issue Recent Advances on Fluorine Chemistry)
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12 pages, 2315 KiB  
Article
Two-Component Rare-Earth Fluoride Materials with Negative Thermal Expansion Based on a Phase Transition-Type Mechanism in 50 RF3-R’F3 (R = La-Lu) Systems
by Boris P. Sobolev and Elena A. Sulyanova
Int. J. Mol. Sci. 2023, 24(18), 14000; https://doi.org/10.3390/ijms241814000 - 12 Sep 2023
Cited by 1 | Viewed by 597
Abstract
The formation of materials with negative thermal expansion (NTE) based on a phase transition-type mechanism (NTE-II) in 50 T–x (temperature–composition) RF3-R’F3 (R = La-Lu) systems out of 105 possible is predicted. [...] Read more.
The formation of materials with negative thermal expansion (NTE) based on a phase transition-type mechanism (NTE-II) in 50 T–x (temperature–composition) RF3-R’F3 (R = La-Lu) systems out of 105 possible is predicted. The components of these systems are “mother” RF3 compounds (R = Pm, Sm, Eu, and Gd) with polymorphic transformations (PolTrs), which occur during heating between the main structural types of RF3: β-(β-YF3) → t-(mineral tysonite LaF3). The PolTr is characterized by a density anomaly: the formula volume (Vform) of the low-temperature modification (Vβ-) is higher than that of the high-temperature modification (Vt-) by a giant value (up to 4.7%). In RF3-R’F3 systems, isomorphic substitutions chemically modify RF3 by forming R1−xR’xF3 solid solutions (ss) based on both modifications. A two-phase composite (β-ss + t-ss) is a two-component NTE-II material with adjustable parameters. The prospects of using the material are estimated using the parameter of the average volume change (ΔV/Vav). The Vav at a fixed gross composition of a system is determined by the β-ss and t-ss decay (synthesis) curves and the temperature T. The regulation of ΔV/Vav is achieved by changing T within a “window ΔT”. The available ΔT values are determined using phase diagrams. A chemical classification (ChCl) translates the search for NTE-II materials from 15 RF3 into an array of 105 RF3-R’F3 systems. Phase diagrams are divided into 10 types of systems (TypeSs), in four of which NTE-II materials are formed. The tables of the systems that comprise these TypeSs are presented. The position of Ttrans of the PolTr on the T scale for a short quasi-system (QS) “from PmF3 to TbF3” determines the interval of the ΔTtrans offset achievable in the RF3-R’F3 systems: from −148 to 1186 ± 10 °C. NTE-II fluoride materials exceed known NTE-II materials by almost three times in this parameter. Equilibrium in RF3-R’F3 systems is established quickly. The number of qualitatively different two-component fluoride materials with the giant NTE-II can be increased by more than ten times compared to RF3 with NTE-II. Full article
(This article belongs to the Special Issue Recent Advances on Fluorine Chemistry)
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