Isostructural Nanocluster Manipulation Reveals Pivotal Role of One Surface Atom in Click Chemistry

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(37)

Published: July 20, 2023

Elucidating single-atom effects on the fundamental properties of nanoparticles is challenging because modifications are typically accompanied by appreciable changes to overall particle's structure. Herein, we report synthesis a [Cu58 H20 PET36 (PPh3 )4 ]2+ (Cu58 ; PET: phenylethanethiolate; PPh3 : triphenylphosphine) nanocluster-an atomically precise nanoparticle-that can be transformed into surface-defective analog [Cu57 ]+ (Cu57 ). Both nanoclusters virtually identical, with five concentric metal shells, save for one missing surface copper atom in Cu57 . Remarkably, loss this single drastically alters reactivity nanocluster. In contrast Cu58 , shows promising activity click chemistry, particularly photoinduced [3+2] azide-alkyne cycloaddition (AAC), which attributed active catalytic site after removal atom. Our study not only presents unique system uncovering effect single-surface modification nanoparticle but also showcases as powerful means designing catalysts.

Language: Английский

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Earth-abundant-metal complexes as photosensitizers in molecular systems for light-driven CO2 reduction

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 500, P. 215529 - 215529

Published: Nov. 6, 2023

Language: Английский

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Catalytic Asymmetric Redox‐Neutral [3+2] Photocycloadditions of Cyclopropyl Ketones with Vinylazaarenes Enabled by Consecutive Photoinduced Electron Transfer

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: April 30, 2024

Abstract Consecutive photoinduced electron transfer (ConPET) is a powerful and atom‐economical protocol to overcome the limitations of intrinsic redox potential visible light‐absorbing photosensitizers, thereby considerably improving substrate reaction types. Likely because such an exothermic single‐electron (SET) process usually does not require aid chiral catalysts, resulting in inevitable racemic background reaction, notably, no enantioselective manifolds have been reported. Herein, we report on viability cooperative ConPET hydrogen‐bonding catalysis for [3+2] photocycloaddition cyclopropyl ketones with vinylazaarenes. In addition enabling first use olefins that preferentially interact this platform paves way efficient synthesis pharmaceutically synthetically important cyclopentyl functionalized by azaarenes high yields, ees dr. The robust capacity method can be further highlighted low loading catalyst (1.0 mol %), good compatibility both 2‐azaarene 3‐pyridine‐based olefins, successful concurrent construction three stereocenters cyclopentane rings involving elusive but all‐carbon quaternary.

Language: Английский

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Radical Cross Coupling and Enantioselective Protonation through Asymmetric Photoredox Catalysis

Advanced Science, Journal Year: 2024, Volume and Issue: 11(12)

Published: Jan. 17, 2024

Abstract An unprecedented enantioselective protonation reaction enabled by photoredox catalytic radical coupling is developed. Under cooperative dicynopyrazine‐derived chromophore (DPZ) as a photosensitizer and chiral phosphoric acid catalyst, Hantzsch ester sacrificial reductant, the transformations between α‐substituted enones cyanoazaarenes or 2‐(chloromethyl)azaaren‐1‐iums can proceed tandem reduction, coupling, process efficiently. Two classes of pharmaceutically important enantioenriched azaarene variants, which contain synthetically versatile ketone‐substituted tertiary carbon stereocenter at β ‐ γ ‐position azaarenes, are synthesized with high yields ees.

Language: Английский

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Efficient Energy and Electron Transfer Photocatalysis with a Coulombic Dyad

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25799 - 25812

Published: Sept. 3, 2024

Photocatalysis holds great promise for changing the way value-added molecules are currently prepared. However, many photocatalytic reactions suffer from quantum yields well below 10%, hampering transition lab-scale to large-scale or even industrial applications. Molecular dyads can be designed such that beneficial properties of inorganic and organic chromophores combined, resulting in milder reaction conditions improved reactions. We have developed a novel approach obtaining advantages molecular without time- resource-consuming synthesis these tailored photocatalysts. Simply by mixing cationic ruthenium complex with an anionic pyrene derivative water salt bichromophore is produced owing electrostatic interactions. The long-lived triplet state obtained static quantitative energy transfer preorganized complex. exploited this so-called Coulombic dyad catalysis similar reactivity higher photostability compared reference photosensitizers several photooxygenations. In addition, it was shown system also used maximize yield photoredox This due intrinsically cage escape after photoinduced electron purely compounds heavy atom-containing molecules. combination laboratory-scale as mechanistic irradiation experiments detailed spectroscopic investigations provided deep insights into easy-to-use photocatalyst class.

Language: Английский

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Energy Decomposition Analysis for excited states: An Extension based on TDDFT

Physical Chemistry Chemical Physics, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Energy decomposition analysis (EDA) is extended by the excited state EDA (exc-EDA) using time-dependent density functional theory (TDDFT). Validated through studies on exciplexes, it demonstrates utility singlet fission in pentacene.

Language: Английский

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Blue Light Irradiated Metal-, Oxidant-, and Base-Free Cross-Dehydrogenative Coupling of C(sp²)–H and N–H Bonds: Amination of Naphthoquinones with Amines

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(11), P. 7401 - 7424

Published: May 12, 2023

Herein, we report a blue-light-driven amination of C(sp2)-H bond naphthoquinones and quinones with the N-H primary secondary amines for synthesis 2-amino-naphthoquinones 2-amino-quinones. The coupling wide array aliphatic, aromatic, chiral, primary, having electron donating (-CH3, -OCH3, -SCH3), withdrawing (-F, -Cl, -Br, -I), CO2H, -OH, -NH2 groups acidic protons selectively occurred to afford C-N coupled in 60-99% yields hydrogen gas as byproduct methanol solvent without using any additional reagents, additives, oxidant under blue light irradiation. Mechanistic insight by DFT computation, controlled experiments, kinetic isotopic effect, substitution effect substrates suggest that reaction proceeds radical pathway which naphthoquinone forms highly oxidizing naphthoquinonyl biradical upon irradiation (457 nm). Consequently, transfer from electron-rich amine an leads anion aminyl cation, followed proton delocalization leading carbon-centered radical. cross-coupling nitrogen radicals bond, subsequent elimination (which was also confirmed GC-TCD), affording 2-amino-1,4-naphthoquinone metal-, reagent-, base-, oxidant-free conditions.

Language: Английский

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Photocatalytic Anti-Markovnikov Hydroamination of Alkenes with Primary Heteroaryl Amines

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(40), P. 21738 - 21744

Published: Oct. 3, 2023

We report a light-driven method for the intermolecular anti-Markovnikov hydroamination of alkenes with primary heteroaryl amines. In this protocol, electron transfer between an amine substrate and excited-state iridium photocatalyst affords aminium radical cation (ARC) intermediate that undergoes C–N bond formation nucleophilic alkene. Integral to reaction success is electronic character amine, wherein increasingly electron-deficient amines generate reactive ARCs. Counteranion-dependent reactivity observed, triflate photocatalysts are employed in place conventional hexafluorophosphate complexes. This exhibits broad functional group tolerance across 55 examples N-alkylated products derived from pharmaceutically relevant

Language: Английский

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Asymmetric Ion-Pairing in Stereoselective Vinyl Polymerization

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(5), P. 3272 - 3284

Published: Feb. 20, 2023

Controlling polymer tacticity is a key consideration in macromolecular synthesis due to the impact of stereochemistry on material's thermomechanical and optical properties. Recently, inspired by work small molecule catalysis, asymmetric ion-pairing has emerged as valuable approach control polymers made through chain growth polymerization vinyl monomers. This Perspective outlines some challenges inherent stereocontrol well highlights recent catalyst development area that enabled both configuration conformation polymers. Several synthetic opportunities mechanistic questions have been identified will expand synthesis.

Language: Английский

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Bifunctional organic photocatalysts for enantioselective visible-light-mediated photocatalysis

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(10), P. 913 - 925

Published: Oct. 2, 2023

Language: Английский

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