Enhanced Three-Component Chloro-/Azido-Fluoroalkylation of Unactivated Alkenes via the Proximity Effect in a Heterogenous Metallaphotocatalyst

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 2180 - 2191

Опубликована: Янв. 22, 2025

Heterogeneous metallaphotocatalytic chemical transformations employing a recyclable catalyst are highly desirable for organic synthesis. However, the rational design and controlled preparation of well-defined, site-isolated metal/photo bifunctional heterogeneous catalysts to achieve this goal remain significant challenge. In study, we demonstrate covalent attachment homogeneous molecular MnSalen complex (where Salen = N,N′-bis(salicylidene)ethylenediamine) onto surface graphitic carbon nitride (CN) via an amide bond visible-light-driven chloro- azido-fluoroalkylation unactivated alkenes. The linkage between CN not only facilitates electron delocalization enhances light-harvesting capabilities photosensitizer but also exerts proximity effect that markedly ability Mn sites capture alkyl radical intermediates during reaction process. A diverse set alkenes could be efficiently azido-fluoroalkylated their corresponding difunctionalized products in moderate high yields with good functional group compatibility. Furthermore, practicability protocol is illustrated through late-stage diversification various bioactive compounds pharmaceuticals. Notably, integrated photocatalyst demonstrates stability can recycled at least 10 times without loss activity selectivity.

Язык: Английский

---

Review of single-atom electrocatalysts for hydrogen and oxygen evolution reactions from water-splitting

Fuel, Год журнала: 2025, Номер 390, С. 134704 - 134704

Опубликована: Фев. 17, 2025

Язык: Английский

---

Tracking Charge Dynamics in a Silver Single-Atom Catalyst During the Light-Driven Oxidation of Benzyl Alcohol to Benzaldehyde

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 5601 - 5613

Опубликована: Март 21, 2025

Understanding charge transfer in light-driven processes is crucial for optimizing the efficiency and performance of a photocatalyst, as directly influences separation migration photogenerated carriers determines overall reaction rate product formation. However, achieving this understanding remains challenging context single-atom photocatalysis. This study addresses gap investigates an Ag-based catalyst (Ag1@CNx) photocatalytic oxidation benzyl alcohol to benzaldehyde. Comprehensive characterization was conducted using battery diffractive, textural, spectroscopic, microscopic methods, confirming crystallinity, porosity, elemental composition, atomic dispersion silver atoms. material displayed efficient selective Density functional theory calculations were used rationalize structure elucidate mechanism, unveiling role holes lowering energy barriers. Time-resolved transient spectroscopic studies monitor dynamics charges reaction, revealing lifetimes behaviors excited states within catalyst. Specifically, introduction atoms led significant enhancement state lifetime, which favors hole-transfer presence alcohol. indicated that photoexcited effectively transferred reactant, thereby driving process oxygen. These mechanistic insights are pivotal spectroscopically elucidating mechanism can be practically applied design photocatalysts more rationally, targeting materials combine both rapid reductive quenching metal.

Язык: Английский

---

An Atomically Dispersed Mn Photocatalyst for Vicinal Dichlorination of Nonactivated Alkenes

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 25, 2025

A novel Mn-based single-atom photocatalyst is disclosed in this study, designed for the dichlorination of alkenes to achieve vicinal dichlorinated products using N-chlorosuccinimide as a mild chlorinating agent, which have widespread applications pest controlling agents, polymers, flame retardants, and pharmaceuticals. In developing innovative catalyst, we achieved atomic dispersion Mn on aryl-amino-substituted graphitic carbon nitride (f-C3N4). This marks first instance heterogeneous version, offering an operationally simple, sustainable, efficient pathway alkenes, including drugs, bioactive compounds, natural products. material was extensively characterized by techniques such UV-vis spectroscopy, X-ray absorption near-edge structure (XANES), extended fine (EXAFS), high-resolution transmission electron microscopy (HR-TEM), photoelectron spectroscopy (XPS), magic-angle spinning (MAS), solid-state nuclear magnetic resonance (ssNMR) understand it at level. Furthermore, mechanistic studies based multiscale molecular modeling, combining classical reactive dynamics (RMD) simulations quantum chemistry (QC) calculations, illustrated that controlled formation Cl radicals from situ formed Mn-Cl bond responsible reaction alkenes. addition, gram-scale reusability tests were also performed demonstrate applicability approach industrial scale.

Язык: Английский

---

XANES-EXAFS spectroscopy for discerning and retrieval of atomic and coordination states of a diverse single-metal-atomic structures

Materials Chemistry and Physics, Год журнала: 2025, Номер unknown, С. 130837 - 130837

Опубликована: Апрель 1, 2025

Язык: Английский

---

Homonuclear/Heteronuclear Bimetallic Conjugated Coordination Polymers with Customized Oxygen Evolution Pathway

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 11, 2025

The reasons for the generally superior performance of synergistic effects in bimetallic catalysts oxygen evolution reaction (OER) are not fully understood, largely due to complexity catalyst structures and challenges associated with synthesizing long-range atomic ordering catalysts. In this study, we present a series two-dimensional (2D) conjugated coordination polymers (c-CPs) involving Co or Ni unambiguous nearly identical geometry electrocatalysis OER, which highly suitable discussions on structure-property correlations. heteronuclear CoNi-PI unexpectedly alters OER catalytic mechanisms from adsorbate mechanism those observed homonuclear CoCo-PI NiNi-PI kinetically faster oxide path mechanism, exhibiting high stability an ultralow overpotential 282 mV even at 100 mA cm-2 Tafel slope approximately 42 dec-1. This study presents extremely rare crystalline excellent properties, promising significant influences development research.

Язык: Английский

---

On the Hunt for Chiral Single-Atom Catalysts

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 6852 - 6873

Опубликована: Апрель 12, 2025

Enantioselective transformations are crucial in various fields, including chemistry, biology, and materials science. Today, the selective production of enantiopure compounds is achieved through asymmetric homogeneous catalysis. Single-atom catalysts (SACs) emerging as a transformative approach enabling heterogenization organometallic complexes effectively bridging gap between heterogeneous Despite their potential, integration SACs into enantioselective processes remains an underexplored area. This perspective offers comprehensive analysis possible strategies for design catalysts, examining how chiral surfaces, modifiers, grafted complexes, spatial confinement techniques can be employed to enhance enantioselectivity. Each these methods presents distinct advantages challenges; example, surfaces modifiers offer potential tailored reactivity but suffer from limited stability selectivity, while provide robust platforms may face issues related scalability synthesis complexity. Spatial show promise enhancing catalyst efficiency constrained by accessibility reproducibility concerns. These lay groundwork adaptation SACs, providing innovative approaches replicate well-defined environments preserving stability, reusability, unique single-atom systems.

Язык: Английский

---

A Career in Catalysis: Gianfranco Pacchioni

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 10271 - 10285

Опубликована: Июнь 2, 2025

Язык: Английский

---