Divergent Photosensitizer Controlled Reactions of 4‐Hydroxycoumarins and Unactivated Olefins: Hydroarylation and Subsequent [2+2] Cycloaddition DOI Open Access

Rui Chang,

Yubing Pang,

Juntao Ye

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 26, 2023

Herein, we report a photoinduced approach for hydroarylation of unactivated olefins using 4-hydroxycoumarins as the arylating reagent. Key to success this reaction is conversion nucleophilic into electrophilic carbon radicals via photocatalytic arene oxidation, which not only circumvents polarity-mismatch issue encountered under ionic conditions but also accommodates broad substrate scope and inhibits side reactions that were previously observed. Moreover, divergent reactivity was achieved by changing photocatalyst, enabling subsequent [2+2] cycloaddition deliver cyclobutane-fused pentacyclic products are otherwise challenging access in high yields with diastereoselectivity. Mechanistic studies have elucidated mechanism origin reactivity.

Language: Английский

Catalyzing Artificial Photosynthesis with TiO2 Heterostructures and Hybrids: Emerging Trends in a Classical yet Contemporary Photocatalyst DOI Open Access
Xiaowen Ruan, Shijie Li,

Chengxiang Huang

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(17)

Published: Oct. 11, 2023

Titanium dioxide (TiO

Citations

71
Structural Motifs in Covalent Organic Frameworks for Photocatalysis DOI

Liyang Qin,

Chengdi Ma,

Jian Zhang

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: March 10, 2024

Abstract Covalent organic frameworks (COFs) attract significant attention due to their ordered, crystalline, porous, metal‐free, and predictable structures. These unique characteristics offer great opportunities for the diffusion transmission of photogenerated charges during photocatalysis. Currently, a considerable number COFs are used as metal‐free semiconductor photocatalysts. This review aims understand relationships between structure photocatalysis performance provides in‐depth insight into synthetic strategy improve performance. Subsequently, focuses on structural motif in sustainable photocatalytic hydrogen evolution, carbon dioxide reduction, peroxide generation, compound transformations. Last, conjunction with progress achieved challenges yet be overcome, candid discussion is undertaken regarding field COF photocatalysis, accompanied by presentation potential research avenues future directions. seeks provide readers comprehensive understanding pivotal role robust guidance innovative utilization

Language: Английский

Citations

57
Progress of Photocapacitors DOI Creative Commons
Natalie Flores‐Díaz, Francesca De Rossi, Aparajita Das

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(15), P. 9327 - 9355

Published: June 9, 2023

In response to the current trend of miniaturization electronic devices and sensors, complementary coupling high-efficiency energy conversion low-loss storage technologies has given rise development photocapacitors (PCs), which combine in a single device. Photovoltaic systems integrated with supercapacitors offer unique light capabilities, resulting improved overall efficiency over past decade. Consequently, researchers have explored wide range device combinations, materials, characterization techniques. This review provides comprehensive overview photocapacitors, including their configurations, operating mechanisms, manufacturing techniques, focus on emerging applications small wireless devices, Internet Things (IoT), Everything (IoE). Furthermore, we highlight importance cutting-edge materials such as metal–organic frameworks (MOFs) organic for supercapacitors, well novel photovoltaics, advancing PCs carbon-free, sustainable society. We also evaluate potential development, prospects, application scenarios this area research.

Language: Английский

Citations

42
Molecular Ratchets and Kinetic Asymmetry: Giving Chemistry Direction DOI Creative Commons
Stefan Borsley, David A. Leigh, Benjamin M. W. Roberts

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: April 3, 2024

Abstract Over the last two decades ratchet mechanisms have transformed understanding and design of stochastic molecular systems—biological, chemical physical—in a move away from mechanical macroscopic analogies that dominated thinking regarding dynamics in 1990s early 2000s (e.g. pistons, springs, etc), to more scale‐relevant concepts underpin out‐of‐equilibrium research sciences today. Ratcheting has established nanotechnology as frontier for energy transduction metabolism, enabled reverse engineering biomolecular machinery, delivering insights into how molecules ‘walk’ track‐based synthesisers operate, acceleration reactions enables be transduced by catalysts (both motor proteins synthetic catalysts), dynamic systems can driven equilibrium through catalysis. The recognition biology, their invention systems, is proving significant areas diverse supramolecular chemistry, covalent DNA nanotechnology, polymer materials science, heterogeneous catalysis, endergonic synthesis, origin life, many other branches science. Put simply, give chemistry direction. Kinetic asymmetry, key feature ratcheting, counterpart structural asymmetry (i.e. chirality). Given ubiquity processes significance behaviour function it surely just fundamentally important. This Review charts recognition, development ratchets, focussing particularly on role which they were originally envisaged elements machinery. Different kinetically asymmetric are compared, consequences discussed. These archetypal examples demonstrate inexorably equilibrium, rather than relax towards it.

Language: Английский

Citations

35
Asymmetric Atomic Dual‐Sites for Photocatalytic CO2 Reduction DOI Creative Commons
Guangri Jia,

Yingchuan Zhang,

Jimmy C. Yu

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(38)

Published: July 23, 2024

Abstract Atomically dispersed active sites in a photocatalyst offer unique advantages such as locally tuned electronic structures, quantum size effects, and maximum utilization of atomic species. Among these, asymmetric dual‐sites are particular interest because their charge distribution generates local built‐in electric potential to enhance separation transfer. Moreover, the dual provide flexibility for tuning complex multielectron multireaction pathways, CO 2 reduction reactions. The coordination opens new possibilities engineering structure–activity–selectivity relationship. This comprehensive overview discusses efficient sustainable photocatalysis processes photocatalytic reduction, focusing on strategic active‐site design future challenges. It serves timely reference development conversion processes, specifically exploring here exemplified by into valuable chemicals.

Language: Английский

Citations

26
Revealing electron numbers-binding energy relationships in heterojunctions via in-situ irradiated XPS DOI
Yukun Li, Yongshang Zhang,

Ruohan Hou

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 356, P. 124223 - 124223

Published: May 22, 2024

Language: Английский

Citations

17
Catalytic Deracemization Reactions DOI
Mouxin Huang, Tianrun Pan,

Xieyang Jiang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 10917 - 10929

Published: May 13, 2023

Deracemization, which converts a racemate into its single enantiomer without separation of the intermediate, has gained renewed interest in asymmetric synthesis with inherent atomic economy and high efficiency. However, this ideal process requires selective energy input delicate reaction design to surmount thermodynamical kinetical constraints. With rapid development catalysis, many catalytic strategies concert exogenous have been exploited facilitate nonspontaneous enantioenrichment. In perspective, we will discuss basic ideas accomplish deracemization, categorized by three major sources including chemical (redox)-, photo- mechanical from attrition. Emphasis be given features underlying deracemization mechanism together perspectives on future development.

Language: Английский

Citations

39
Emerging Trends in Copper-Promoted Radical-Involved C–O Bond Formations DOI

Peng‐Zi Wang,

Jia‐Rong Chen, Wen‐Jing Xiao

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(32), P. 17527 - 17550

Published: Aug. 2, 2023

The C–O bond is ubiquitous in biologically active molecules, pharmaceutical agents, and functional materials, thereby making it an important group. Consequently, the development of bond-forming reactions using catalytic strategies has become increasingly research topic organic synthesis because more conventional methods involving strong base acid have many limitations. In contrast to ionic-pathway-based methods, copper-promoted radical-mediated formation experiencing a surge interest owing renaissance free-radical chemistry photoredox catalysis. This Perspective highlights appraises state-of-the-art techniques this burgeoning field. contents are organized according different reaction types working models.

Language: Английский

Citations

39
Ratcheting synthesis DOI
Stefan Borsley, James Gallagher, David A. Leigh

et al.

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 8(1), P. 8 - 29

Published: Dec. 15, 2023

Language: Английский

Citations

30
Radical thioesterification via nickel-catalysed sensitized electron transfer DOI Creative Commons
Huamin Wang, Zhao Liu, Ankita Das

et al.

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(11), P. 1116 - 1126

Published: July 10, 2023

Abstract Multi-catalytic reaction modes have attracted widespread attention in synthetic chemistry. The merger of nickel catalysis with photoredox has offered a powerful platform for synthesis molecules attractive properties. Nonetheless, the conceptual development nickel-catalysed, sensitized electron transfer is pivotal relevance, but still greatly limited. Here we describe radical cross-thioesterification process by nickel-catalysed transfer. strategy can produce diverse methyl thioesters, which are not only found natural products, materials and pharmaceuticals also precursors chemistry biological processes. This catalytic mode features high chemoselectivity, good functional group tolerance excellent scalability. Perhaps more important was finding that various drugs amino acids were successfully functionalized this system. Experimental studies, nanosecond transient spectroscopic analysis, density theory calculations reveal photocatalytic transfer, energy plays an essential role thioesterification reaction.

Language: Английский

Citations

26