PF₆⁻ Pseudohalides Anion Based Metal‐Free Perovskite Single Crystal for Stable X‐Ray Detector to Attain Record Sensitivity

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(25)

Published: March 27, 2023

Metal-free perovskites (MFPs) possess excellent photophysical properties of while avoiding the introduction toxic metal ions and organic solvents, have been expanded to X-ray detection. However, iodine-based high-performance MFPs are tended oxidation, corrosion, uncontrolled ion migration, resulting in poor material stability device performance. Herein, strongly electronegative PF6- pseudohalide is used fabricate large-size MDABCO-NH4 (PF6 )3 (MDBACO = methyl-N'-diazabicyclo[2.2.2]octonium) single crystals (SCs) for solving problems iodine ions. After pseudohalides, Coulomb interaction hydrogen bonding strength enhanced alleviate ion-migration problems. Moreover, combined with theoretical calculations, pseudohalides increase barrier, affect contribution its components energy band a broadening bandgap. Meanwhile, improved physical properties, such as large activation ionic high resistivity, low current drift, further expand application low-dose sensitive Finally, detector based on SCs achieves sensitivity 2078 µC Gyair-1 cm-2 (highest among metal-free SCs-based detectors) lowest detectable dose rate (16.3 nGyair s-1 ). This work has selection detectors somewhat advanced development devices.

Language: Английский

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Catalyst-Free gem-Difluorination/Spirocyclization of Indole-2-carboxamides: Synthesis of C2-Spiroindoline Derivatives

Organic Letters, Journal Year: 2023, Volume and Issue: 25(48), P. 8771 - 8776

Published: Nov. 28, 2023

A catalyst-free gem-difluorination/spirocyclization reaction has been successfully developed for the synthesis of gem-difluorinated C2-spiroindoline derivatives from indole-2-carboxamides. The resulting C2-spiroindolines can be easily converted into 2-spiropseudoindoxyls through hydrolysis. This method offers benefits simple operation, convenient access to raw materials, and mild conditions. Dual function Selectfluor in this is noteworthy as it serve both a fluorinating agent an alkaline accelerator precursor.

Language: Английский

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Research Progress on Palladium-Catalyzed Difluoromethyl Arylation

Journal of Organic Chemistry Research, Journal Year: 2025, Volume and Issue: 13(01), P. 21 - 34

Published: Jan. 1, 2025

Language: Английский

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Regio‐ and Z‐Selective Alkyne Hydroamination and Hydrophenoxylation using Tetrafluoro‐λ⁶‐Sulfanyl Alkynes under Superbasic, Naked Anion Conditions

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(33)

Published: June 25, 2023

Alkyne hydroamination is an effective approach for the production of enamines and enamine-containing N-heterocycles. However, stereoselectivity control a considerable challenge in this reaction because electronic repulsion between incoming nitrogen lone pair alkyne π-system. Herein, we propose methodology involving β-regio- Z-selective by using tetrafluoro-λ6 -sulfanyl (SF4 ) alkynes under superbasic, naked anion conditions. The compatible with wide variety N-heterocycles, including indoles, carbazoles, pyrazoles, imidazoles, selectively furnishes SF4 -linked Z-vinyl β-regioselectively. Moreover, method can be extended to β- Z-controlled, base-mediated hydrophenoxylation phenols provide ethers high yields. As unit has attracted attention as bioisostere alkynes, p-benzenes, bicyclo[1.1.1]pentyl (BCP) groups, cubanes medicinal chemistry, chemistry represents creating novel drug candidates incorporating -containing molecules.

Language: Английский

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Natural Fragment Bond Orbital Method for Inter-Fragment Covalent Interaction Analysis

Published: June 12, 2024

A complex chemical system is often examined based on their fragments, so fragment-based analysis the key to understanding. We report natural fragment bond orbital (NFBO) method for inter-fragment bonding interaction analysis, as an extension well-known method. NFBOs together with corresponding hybrid orbitals (NFHOs) allow us derive local and anti-bonding among fragments from delocalized canonical molecular orbitals. In this paper, we provide algorithm finding showcase its application several chemically interesting systems featuring significant interactions. Through these examples, NFBO shown be a powerful tool which analyze molecules possessing strong

Language: Английский

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Natural Fragment Bond Orbital Method for Interfragment Bonding Interaction Analysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(50), P. 34591 - 34599

Published: Dec. 10, 2024

A complex chemical system is often examined based on their fragments, so fragment-based analysis the key to understanding. We report natural fragment bond orbital (NFBO) method for interfragment bonding interaction analysis, as an extension well-known method. NFBOs together with corresponding hybrid orbitals (NFHOs) allow us derive local and antibonding among fragments from delocalized canonical molecular orbitals. In this paper, we provide algorithm finding showcase its application several chemically interesting systems featuring significant interactions. Through these examples, NFBO shown be a powerful tool which analyze electronic structures of molecules possessing strong

Language: Английский

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Transition-State Stabilization by Secondary Orbital Interactions between Fluoroalkyl Ligands and Palladium During Reductive Elimination from Palladium(aryl)(fluoroalkyl) Complexes

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(19), P. 12810 - 12825

Published: Sept. 18, 2023

Palladium-catalyzed fluoroalkylations of aryl halides are valuable reactions for the synthesis fluorinated, biologically active molecules. Reductive elimination from an intermediate Pd(aryl)(fluoroalkyl) complex is step that forms C(aryl)–C(fluoroalkyl) bond, and this typically requires higher temperatures proceeds with slower rates than reductive nonfluorinated alkylarenes analogous Pd(aryl)(alkyl) complexes. The experimental correlate poorly common parameters, such as steric property or electron-withdrawing ability fluoroalkyl ligand, making prediction rational design Pd-catalyzed difficult. Therefore, a systematic study features ligands affect barrier to key step, including properties, secondary interactions, necessary future development fluoroalkylation occur under milder conditions tolerate additional types reagents. We report computational studies effect (RF) ligand on barriers Pd(aryl)(RF) complexes (RF = CF2CN, CF2C(O)Me, etc.) containing bidentate di-tert-butyl(2-methoxyphenyl)phosphine (L). computed Gibbs free-energy these suggest fluoroalkylarenes should form quickly at room temperature we studied, excluding RF CF3, CF2Me, C2F5, CF2CFMe2, CF2Et, CF2iPr, CF2tBu. Analyses transition-state structures by natural bond orbital (NBO) independent gradient model (IGMH) approaches reveal interactions between Pd center hydrogen atom π-acid bonded α-carbon stabilize lowest-energy transition states Comparisons conformers magnitude stabilizations 4.7–9.9 kcal/mol. In absence more leads less ligand. Computations para-substituted groups palladium electron-rich tend be lower those when can engage in metal center. However, do not depend electronic properties

Language: Английский

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Synthesis of Pyridine-SF4-Alkynes via Light-Promoted Radical Coupling of Pyridine-SF4-Chlorides and EBX Reagents

Bulletin of the Chemical Society of Japan, Journal Year: 2022, Volume and Issue: 96(2), P. 110 - 112

Published: Dec. 23, 2022

Abstract Pyridine-tetrafluoro-λ6-sulfanyl-alkynes have emerged as building blocks for synthesizing linearly-linked pyridine-heterocycles. They are prepared via a two-step procedure comprising the radical addition of pyridine-tetrafluoro-λ6-sulfanyl-chlorides and alkynes subsequent base-promoted elimination HCl. Herein we developed straightforward alternative synthesis coupling with ethynylbenziodoxolone reagents under LED irradiation.

Language: Английский

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Synthesis of (Bromodifluoromethyl)trimethylsilane and Its Applications in Organic Synthesis

Chinese Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 43(10), P. 3491 - 3491

Published: Jan. 1, 2023

Bromodifluoromethyl trimethylsilane (TMSCF2Br) has proved to be an important difluoromethyl(alkyl)ation reagent that is widely applied in organic synthesis over the past decade, since it was used as a difluorocarbene precursor 2011.This review aims provide briefly summary for of TMSCF2Br, and introduce recent advances applications TMSCF2Br or trimethylsilyldifluoromethyl radical developing various difluoromethyl(alkyl)ations different kinds substrates.Meanwhile, activation ways possible mechanism, well its advantages disadvantages each kind reactions are detailedly disccussed, which might some references inspiration researchers engaged fluorine chemistry.

Language: Английский

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Three-component approach to modular synthesis of tetra-substituted furans and pyrroles

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(9), P. 2554 - 2560

Published: Jan. 1, 2024

A three-component one-pot reaction of TMSCF 2 Br, p -QMs and 1,3-dicarbonyl compounds derivatives was developed. series densely functionalized tetra-substituted furans pyrroles were constructed with excellent chemoselectivities.

Language: Английский

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