Enantioselective photochemical reactions within the confined cavities of supramolecular assemblies DOI Open Access
Yiwen Su, Cheng Pan,

Tao-Yue Sun

et al.

Chemical Synthesis, Journal Year: 2024, Volume and Issue: 4(4)

Published: Oct. 14, 2024

Compared to bulk solvents, reactions in the confined spaces of supramolecular self-assemblies feature rate acceleration, high efficiency and substrate selectivity. These advantages lead efficient catalytic excellent selectivity enantioselective photochemical transformations. During last few years, photocatalysis has developed into one most powerful strategies construct enantioenriched chiral compounds. In this review, recent advances taking place within assemblies are summarized, with an emphasis on specific modes chemical Organization data follows a subdivision according host reaction type. At last, current limitations future research orientation field discussed.

Language: Английский

Room-temperature aerobic oxidation of alcohols into carbonyl compounds using VO@GO catalyst DOI

S. Krishnam Raju,

Kothanahally S. Sharath Kumar, Yarabahally R. Girish

et al.

Synthetic Communications, Journal Year: 2025, Volume and Issue: unknown, P. 1 - 11

Published: Feb. 19, 2025

Language: Английский

Citations

0

Modulating N‐Heterocyclic Microenvironment in β‐Ketoenamine Covalent Organic Frameworks to Boost Overall Photosynthesis of H2O2 DOI

Yangpeng Zhang,

Youting Wu, Hailing Ma

et al.

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 28, 2025

Abstract Covalent Organic Frameworks (COFs) have emerged as promising platforms for photocatalytic synthesis of hydrogen peroxide (H 2 O ) due to their tunable chemical compositions and efficient catalytic functionalities. Inspired by the role microenvironment in enzyme catalysis, this study introduces various N‐heterocyclic species into β ‐ketoenamine COFs (N x ‐COFs, where N represents number nitrogen atoms N‐heterocycle) regulate around sites on acceptor‐donor‐acceptor (A‐D‐A) foroverall H photosynthesis pure water. The ‐COFs exhibit distinct photosynthetic rates following sequence 3 ‐COF > 1 0 ‐COF, with triazine structure showing highest generation rate (4881 µmol h −1 g decent solar‐to‐chemical conversion (SCC) efficiency (0.413%), surpassing many existing COF‐based catalysts. In situ characterization theoretical calculations support experimental results, revealing that promote through both an indirect stepwise single‐electron oxygen reduction reaction (1e − ORR) mechanism a direct two‐electron water oxidation (2e WOR) pathway. This advances design paradigm photocatalysts modulating within A‐D‐A COFs, paving way development more robust systems overall .

Language: Английский

Citations

0

Asymmetric Cascade Photocycloaddition-Acyloin Rearrangement Enabled by Cage-Confined Visible-Light Catalysis DOI
Jie Chen, Yu‐Lin Lu,

Yongxian Huang

et al.

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

Published: April 8, 2025

Enzymatic catalysis in biological systems is characterized by the specific pocket confinement imposed various protein matrixes, enabling synthesis of a diverse array functional biomolecules. Development new catalysts that incorporate multiple catalytic centers within enzyme-mimic confined spaces presents meaningful yet challenging project for synthetic chemists. Here, we present our recent achievement synthesizing chiral photosensitive metal-organic cage (cPMOC), Δ4-/Λ4-MOC-68-Ru4, which possesses pockets can facilitate visible-light-induced asymmetric cascade intermolecular [2 + 2] cycloaddition/acyloin rearrangement first time. The current photochemical transformation affords bicyclo[3.2.1]octanes with opposite regiospecificity contrast to well-established thermodynamically favored [3 cycloaddition transformations similar reaction counterparts. distinctive size 2 inhibits dimerization α,β-unsaturated ketones and promotes heterocycloaddition between ketone smaller cyclic 1,2-dione, underscoring critical role microenvironmental shape guest binding determining reactivity.

Language: Английский

Citations

0

Sol-Gel Heterogeneization of an Ir(III) Complex for Sustainable Visible-Light Redox Photocatalysis DOI Creative Commons

Janira Herce,

Mónica Martínez-Aguirre,

Javier Gómez-Benito

et al.

Molecules, Journal Year: 2025, Volume and Issue: 30(8), P. 1680 - 1680

Published: April 9, 2025

Photocatalysis is a key strategy for the development of sustainable solar-driven chemical processes. In this work, we report synthesis and characterization novel organometallo-ionosilica material derived from self-condensation an alcoxysilane functionalized Ir(III) complex. acetonitrile suspension, retains photophysical properties its precursor in solution same solvent, together with significant absorption visible between 400 500 nm. As heterogeneous photocatalyst, showed high efficiency reductive dehalogenation 2-bromoacetophenone under blue light irradiation, achieving yields conversion about 90%, excellent recyclability seven catalytic cycles, retaining more than 70% efficiency. All these self-condensed highlight potential as efficient photocatalyst applications organic redox

Language: Английский

Citations

0

A Redox‐Active Phenothiazine‐based Pd2L4‐Type Coordination Cage and Its Isolable Crystalline Polyradical Cations DOI
Bin Huang,

Manfei Zhou,

Qiong‐Yan Hong

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 14, 2024

Polyradical cages are of great interest because they show very fascinating physical and chemical properties, but many challenges remain, especially for their synthesis characterization. Herein, we present the a polyradical cation cage 1

Language: Английский

Citations

2

Hydrazone‐Linked Donor‐Acceptor Covalent Organic Polymer as a Heterogeneous Photocatalyst for C‐S Bond Formation DOI

Mohit Mohit,

Sunil Kumar, K. R. Justin Thomas

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: July 22, 2024

Abstract In the realm of solar energy utilization, there is a growing focus on designing and implementing effective photocatalytic systems, for conversion into valuable chemical fuels. The potential Covalent Organic Polymers (COPs) as photocatalysts visible‐light‐driven organic transformation has been widely investigated, positioning them promising candidates in this field. design COPs, introducing donor‐acceptor arrangement facilitates transfer electrons from donor to acceptor, creating charge complex leading enhanced conductivity improved separation. Here we present novel hydrazone‐linked covalent polymer ETBC‐PyHz containing TPE pyridine acceptor. Utilizing this, an efficient method developed oxidative cross‐coupling reaction involving C−S bond formation. This process involves arylhydrazines arenethiols, results production unsymmetrical diaryl sulfides via formation aryl thioarene radicals. holds significant importance because byproducts produced during are nitrogen water, making it environmentally benign.

Language: Английский

Citations

2

Iron-copper bimetallic photo-Fenton system promoted photothermal-hydrogen peroxide production for efficient low-temperature wastewater treatment DOI
Bo Ren, Zipeng Xing, Na Zhang

et al.

Journal of Colloid and Interface Science, Journal Year: 2024, Volume and Issue: 677, P. 882 - 895

Published: Aug. 22, 2024

Language: Английский

Citations

2

Reserving Electrons in Cofactor Decorated Coordination Capsules for Biomimetic Electrosynthesis of α-Hydroxy/amino Esters DOI
Huali Wang, Yu Zhang, Guanfeng Ji

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 24, 2024

Sustainable electricity-to-chemical conversion via the utilization of artificial catalysts inspired by redox biological systems holds great significance for catalyzing synthesis. Herein, we develop a biomimetic electrosynthesis strategy mediated nicotinamide adenine dinucleotide (NADH) mimic-containing coordination capsule efficiently producing α-hydroxy/amino esters. The saturated metal centers worked as an electron relay to consecutively accept single electrons while donating two NAD

Language: Английский

Citations

2

Modulating the Aggregation States of a Pd6L4 Cage for Selectivity Flipping during the Stereo‐Divergent Semi‐Hydrogenation of Alkynes DOI
Wei Zhong,

Xu Jing,

Zhao Song

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 6, 2024

Abstract An enzyme‐mimicking catalytic system has been established using a singular palladium‐based octahedral cage as the supramolecular reactor, deftly unlocking off‐on‐off selectivity in semi‐hydrogenation of alkynes. Water serves critical regulator, modulating catalyst states, reaction rates, and endpoints. The choice solvent influences activity host–guest binding types homogeneous heterogeneous catalysis, effectively modifying steps involved Z → E isomerization during Kinetic inhibition experiments indicate that mimics activation characteristics enzymes towards substrates, enabling selective transformations within confined environment. utility this switchable cage‐confined catalysis demonstrated synthesis modification complex biologically active molecules with controllable / selectivity. This work sheds light on design control artificial counterparts enzymes, offering fundamental insights into factors influencing biological macromolecules.

Language: Английский

Citations

2

Stereochemical Control of Redox CoII/CoIII-Cages with Switchable Cotton Effects Based on Labile-Static States DOI
Yu‐Lin Lu,

Kai Wu,

Yin‐Hui Huang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 20414 - 20424

Published: July 10, 2024

The structural dynamics of artificial assemblies, in aspects such as molecular recognition and transformation, provide us with a blueprint to achieve bioinspired applications. Here, we describe the assembly redox-switchable chiral metal-organic cages Λ

Language: Английский

Citations

1