Chalcogen Bonding Catalysis: Tellurium, the Last Frontier?

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(69)

Published: Sept. 25, 2023

Chalcogen bonding (ChB) is the non-covalent interaction occurring between chalcogen atoms as Lewis acid sites and or groups of able to behave bases through their lone pair π electrons. Analogously its sister halogen bonding, high directionality this was implemented for precise structural organizations in solid state solution. Regarding catalysis, ChB now accepted a new mode activation demonstrated by increased number examples last five years. In family catalysts, those based on tellurium rapidly appeared overcome lighter sulfur selenium counterparts. review, we highlight properties tellurium-based derivatives solution summarize start-of-the-art applications catalysis.

Language: Английский

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Molecular‐Additive‐Assisted Tellurium Homogenization in ZnSeTe Quantum Dots

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(45)

Published: July 14, 2023

Abstract Addition of aqueous hydrohalic acids during the synthesis colloidal quantum dots (QDs) is widely employed to achieve high‐quality QDs. However, this reliance on use solutions incompatible with oxygen‐ and water‐sensitive precursors such as those used in Te‐alloyed ZnSe Herein, it shown that incompatibility leads phase segregation into Te‐rich Te‐poor regions, causing spectral broadening luminescence peak shifting under high laser irradiation applied electrical bias. Here, a synthetic strategy produce anhydrous‐HF situ by using benzenecarbonyl fluoride (BF) chemical additive reported. Through 19 F NMR spectroscopy, found BF reacts surfactants tandem, ultimately producing intermediary F···H···trioctylamine adducts. These act pseudo‐HF source releases anhydrous HF. The controlled release HF nucleation growth steps homogenizes Te distribution ZnSeTe lattice, leading spectrally stable blue‐emitting QDs increasing flux from ≈3 µW ≈12 mW bias 2.6 10 V. Single‐dot photoluminescence (PL) spectroscopy analyses absorption, PL transient absorption spectra together density functional theory point role homogenizer.

Language: Английский

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A Hexavalent Tellurium-Based Chalcogen Bonding Catalysis Platform: High Catalytic Activity and Controlling of Selectivity

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

Herein, we describe a hexavalent tellurium-based chalcogen bonding catalysis platform capable of addressing reactivity and selectivity issues. This research demonstrates that tellurium salts can serve as class highly active catalysts for the first time. The centers in these have only one exposed interaction site, thus providing favorable condition controlling reaction selectivity. advantages were demonstrated by their remarkable catalytic activity cyanidation difluorocyclopropenes through C-F bond activation, which otherwise low reactive under strong Lewis acids or inaccessible representative divalent/tetravalent donors. catalyst was further highlighted its capability to address previously unresolved problem associated with acid approach, upon using some less silyl enol ethers nucleophiles functionalization difluorocyclopropenes. generality this versatile application different systems. differentiate two similar free OH groups glycosyl acceptors achieve excellent regio- stereoselectivity synthesis disaccharides, tetravalent gave Mechanistic investigation suggests catalyst-glycosyl donor-acceptor ternary supramolecular complex is operative.

Language: Английский

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Telluronium‐Catalyzed Halogenation Reactions: Chalcogen‐Bond Activation of N‐Halosuccinimides and Catalysis

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(43)

Published: May 24, 2024

The ability of triaryltelluronium salts to interact with N-halosuccinimides (NXS) through chalcogen bonding (ChB) in the solid state and solution is demonstrated herein. Cocrystals bearing two CF

Language: Английский

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Neutral Chalcogen Bonding Enabled Photoinduced Cross‐Electrophile C—S/Se Coupling of Aryl Iodides via S_RN1 Process

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Comprehensive Summary Cross‐coupling reactions between aryl halides and thiolates or selenolates typically require transition metals, photocatalysts, strong bases, or/and malodorous thiols/selenols, with various mechanisms proposed. This study aims to leverage a new application of neutral ChB address these challenges enable very simple photoinduced cross‐electrophile C—S/Se coupling using readily available chalcogen electrophiles. Mechanistic investigations have revealed the important role in facilitating single electron transfer processes, thereby enabling generation thiolates/selenolates from stable electrophiles α ‐aminoalkyl radicals, which possess capability abstract halogen atoms iodides. Moreover, provided support for radical nucleophilic substitution mechanism.

Language: Английский

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Te⋯I secondary-bonding interactions in crystals containing tellurium(ii), tellurium(iv) and iodide atoms: supramolecular aggregation patterns, nature of the non-covalent interactions and energy considerations

CrystEngComm, Journal Year: 2024, Volume and Issue: 26(21), P. 2784 - 2795

Published: Jan. 1, 2024

The importance of σ-hole bonding is emphasised in a series mixed tellurium( ii )/tellurium( iv )/iodide crystals.

Language: Английский

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Supramolecular assembly governed by tetrel, CN⋅⋅⋅π and other weak noncovalent interactions in two acrylonitrile derivatives with D-π-A topology: crystallography, optical properties and theoretical studies

Journal of Molecular Structure, Journal Year: 2024, Volume and Issue: 1320, P. 139650 - 139650

Published: Aug. 17, 2024

Language: Английский

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Chalcogen Bond Catalysis with Telluronium Cations for Bromination Reaction: Importance of Electrostatic and Polarization Effects

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(71)

Published: Sept. 25, 2023

Recently, chalcogen bond catalysts with telluronium cations have garnered considerable attention in organic reactions. In this work, catalysis on the bromination reaction of anisole N-bromosuccinimide (NBS) cationic has been explored density functional theory (DFT). The catalytic is divided into two stages: bromine transfer step and proton step. Based computational results, one can find rate-determining Moreover, present study elucidates that a stronger between NBS will give better performance. Additionally, work also clarified importance electrostatic polarization effects oxygen atom Te catalyst reaction. are significantly influenced by electron-withdrawing ability substitution groups catalysts. structure-property relationship strength bond, effect, effect performance established for design more efficient

Language: Английский

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Affinity of Telluronium Chalcogen Bond Donors for Lewis Bases in Solution: A Critical Experimental‐Theoretical Joint Study

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(7)

Published: Nov. 16, 2023

Telluronium salts [Ar

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Computational Insight into the Nature and Strength of the π-Hole Type Chalcogen∙∙∙Chalcogen Interactions in the XO2∙∙∙CH3YCH3 Complexes (X = S, Se, Te; Y = O, S, Se, Te)

International Journal of Molecular Sciences, Journal Year: 2023, Volume and Issue: 24(22), P. 16193 - 16193

Published: Nov. 10, 2023

In recent years, the non-covalent interactions between chalcogen centers have aroused substantial research interest because of their potential applications in organocatalysis, materials science, drug design, biological systems, crystal engineering, and molecular recognition. However, studies on π-hole-type chalcogen∙∙∙chalcogen are scarcely reported literature. Herein, intermolecular model complexes formed XO2 (X = S, Se, Te) CH3YCH3 (Y O, were systematically studied by using quantum chemical computations. The stabilized via one primary X∙∙∙Y bond (ChB) secondary C-H∙∙∙O hydrogen bonds. binding energies range -21.6~-60.4 kJ/mol. distances significantly smaller than sum van der Waals radii corresponding two atoms. ChBs all except for SO2∙∙∙CH3OCH3 complex strong strength display a partial covalent character revealed conducting theory atoms molecules (QTAIM), interaction plot (NCIplot), natural orbital (NBO) analyses. symmetry-adapted perturbation (SAPT) analysis discloses that primarily dominated electrostatic component.

Language: Английский

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