Photocatalysis Meets Confinement: An Emerging Opportunity for Photoinduced Organic Transformations

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(15)

Опубликована: Янв. 19, 2024

Abstract The self‐assembled metal‐organic cages (MOCs) have been evolved as a paradigm of enzyme‐mimic catalysts since they are able to synergize multifunctionalities inherent in metal and organic components constitute microenvironments characteristic enzymatic spatial confinement versatile host–guest interactions, thus facilitating unconventional transformations via unique driving‐forces such weak noncovalent binding electron/energy transfer. Recently, MOC‐based photoreactors emerged burgeoning platform supramolecular photocatalysis, displaying anomalous reactivities selectivities distinct from bulk solution. This perspective recaps two decades journey the photoinduced radical reactions by using photoactive (PMOCs) artificial reactors, outlining how cage‐confined photocatalysis was stoichiometric photoreactions photocatalytic turnover, high‐energy UV‐irradiation sustainable visible‐light photoactivation, simple multi‐level chemo‐ stereoselectivities. We will focus on PMOCs that merge structural functional biomimicry into single‐cage behave multi‐role photoreactors, emphasizing their potentials tackling current challenges through single‐electron transfer (SET) or energy (EnT) pathways simple, green while feasible manner.

Язык: Английский

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Integrating Photoactive Ligands into Crystalline Ultrathin 2D Metal–Organic Framework Nanosheets for Efficient Photoinduced Energy Transfer

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(2), С. 1491 - 1500

Опубликована: Янв. 3, 2024

3D metal–organic frameworks (MOFs) have gained attention as heterogeneous photocatalysts due to their porosity and unique host–guest interactions. Despite potential, MOFs face challenges, such inefficient mass transport limited light penetration in photoinduced energy transfer processes. Recent advancements organic photocatalysis uncovered a variety of photoactive cores, while heterogenization remains an underexplored area with great potential build MOFs. This gap is bridged by incorporating cores into 2D MOF nanosheets, process that merges the realms small-molecule photochemistry chemistry. approach results recyclable exhibit improved efficiency. research demonstrates bottom-up synthetic method for embedding successfully producing variants PCN-641-NS, PCN-643-NS, PCN-644-NS. The conditions were systematically studied optimize crystallinity morphology these nanosheets. Enhanced interactions structures confirmed through various techniques, particularly solid-state NMR studies. Additionally, efficiency nanosheets was evidenced photoborylation reactions generation reactive oxygen species (ROS).

Язык: Английский

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Bridging the Homogeneous and Heterogeneous Catalysis by Supramolecular Metal‐Organic Cages with Varied Packing Modes

Advanced Materials, Год журнала: 2024, Номер 36(15)

Опубликована: Янв. 16, 2024

Abstract Integrating the advantages of homogeneous and heterogeneous catalysis has proved to be an optimal strategy for developing catalytic systems with high efficiency, selectivity, recoverability. Supramolecular metal‐organic cages (MOCs), assembled by coordination metal ions organic linkers into discrete molecules, have performed solvent processability due their tunable packing modes, endowing them potential act as or catalysts in different systems. Here, design synthesis a series stable {Cu 3 } cluster‐based tetrahedral MOCs varied structures are reported. These MOCs, catalysts, not only show activity selectivity regardless substrate size during CO 2 cycloaddition reaction, but also can easily recovered from reaction media through separating products co‐catalysts one‐step work‐up. This is because that these solubilities solvents solid state. Moreover, entire system very clean, purity cyclic carbonates 97% without further purification. work provides unique novel supramolecular used recycled manner.

Язык: Английский

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Recent Advances in Carborane-Based Crystalline Porous Materials

Molecules, Год журнала: 2024, Номер 29(16), С. 3916 - 3916

Опубликована: Авг. 19, 2024

The field of carborane research has witnessed continuous development, leading to the construction and development a diverse range crystalline porous materials for various applications. Moreover, innovative synthetic approaches are expanding in this field. Since first report carborane-based (CCPMs) 2007, synthesis ligands, particularly through methods, consistently posed significant challenge discovering new structures CCPMs. This paper provides comprehensive summary recent advances CCPMs, along with their applications different domains. primary challenges future opportunities expected stimulate further multidisciplinary

Язык: Английский

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Photoactive Single-Site Tin(IV) Catalyst for 5-Hydroxymethylfurfural Production from Sugars

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 2950 - 2958

Опубликована: Фев. 4, 2025

Язык: Английский

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Integrating Photoactive Ligands into Dimension-Reduced Metal–Organic Frameworks: Harnessing the Power of Organic Photocatalysts

Accounts of Materials Research, Год журнала: 2024, Номер 5(3), С. 236 - 248

Опубликована: Фев. 9, 2024

ConspectusThis Account aims to concisely summarize recent advancements in the field of photocatalysis, with a particular focus on dimension-reduced metal–organic nanomaterials, including coordination cages and 2D structures. Metal–organic frameworks (MOFs), known for their high crystallinity, porosity, well-determined structures, are at forefront this research. They offer unique confined environment that is optimal enhancing host–guest interactions. This, turn, leads highly selective efficient catalytic reactions. The ability MOFs provide structured controlled has revolutionized way we approach processes, especially terms efficiency selectivity. However, significant challenge emerged use traditional 3-dimensional bulk limitation mass transport. This often results reduced efficiency, hindering practical applicability industrial scenarios. To address these challenges, researchers have taken novel turn toward exploring 0-dimensional (0D) porous 2-dimensional (2D) MOF-derived nanosheets. These structures exhibit improved transport capabilities more exposed centers, thereby circumventing issues faced by 3D counterparts. shown great promise overcoming limitations pore clogging, common issue MOFs, thus paving scalable processes.Section 2 our paper delves deeper into design functionalities MOF section particularly focused theoretical technical approaches necessary understand utilize materials effectively. We discuss various methods, studying redox cycles through electrochemical photochemical intricate dynamics chemistry. Additionally, highlights latest spectroscopic computational techniques been instrumental research efforts. enabled scientists investigate active sites within providing insights mechanisms potential applications. In 3 Account, discussion availability photoactive ligands framework materials. addition structural innovations, account also realm introducing small-molecule organic photocatalysts. pivotal understanding underlying chemistry innovative employed development elaborate synthetic methodologies, choice functional groups, applications Despite inherent such as short excited-state lifespans difficulties recycling, photocatalysts vast effective transformations. By integrating small molecules 0D frameworks, chemists able significantly enhance stability.In conclusion, elucidate principles explore reliable characterization techniques, inspire catalysts. goal achieve catalysts heightened selectivity activity, which can revolutionize processes contribute sustainable development. Through comprehensive overview, hope foundational future rapidly evolving field, guiding new discoveries innovations.

Язык: Английский

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Increasing the stability of calixarene-capped porous cages through coordination sphere tuning

Dalton Transactions, Год журнала: 2024, Номер 53(9), С. 4005 - 4009

Опубликована: Янв. 1, 2024

Chemically and thermally stable permanently porous coordination cages are appealing candidates for separations, catalysis, as the component of new liquids.

Язык: Английский

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Enantiopure trigonal bipyramidal coordination cages templated by in situ self-organized D2h-symmetric anions

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июль 4, 2024

Abstract The control of a molecule’s geometry, chirality, and physical properties has long been challenging pursuit. Our study introduces dependable method for assembling D 3 -symmetric trigonal bipyramidal coordination cages. Specifically, 2h anions, like oxalate chloranilic self-organize around metal ion to form chiral-at-metal anionic complexes, which template the formation chirality bipyramid is determined by point chiral amines used in forming ligands. Additionally, these cages exhibit selectivity included template. broadly applicable various ligand systems, enabling construction larger when are employed. Furthermore, we successfully produce enantiopure with anthracene-containing backbones using this approach, would be otherwise infeasible. These circularly polarized luminescence, modulable through reversible photo-oxygenation anthracenes.

Язык: Английский

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Metallocage Photoredox Confined Synergistic Catalysis on 1,3-Rearrangement Reaction

ACS Catalysis, Год журнала: 2024, Номер 14(17), С. 12793 - 12805

Опубликована: Авг. 9, 2024

The realm of catalytic chemistry has witnessed notable advancements through the integration photoredox confined synergistic catalysis, a method that synergizes benefits and catalysis. This innovative approach facilitates generation reactive intermediates via reactions, while microenvironment tailors distinct selectivity processes. Despite its progress, several aspects, including intricacies encapsulation process, characteristics underlying mechanisms, remain to be fully elucidated. In order answer these questions, this work investigated 1,3-rearrangement reaction mechanism cinnamyl ammonium bromide within metallocage (K12[Ga4L6], L = N,N′-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene). Through molecular dynamics simulations, process was meticulously analyzed determine initial host–guest assembly structure. Subsequent quantum chemical calculations shed light on mechanistic details nuances 1,3-rearrangement. investigation reveals radical unfolds in two pivotal stages: breaking C–N bond, accompanied by an electronic state conversion facilitated formation conducted space metallocage. Notably, catalysis plays crucial role altering product selectivity, demonstrating potential strategy guide pathways with enhanced precision. study not only clarifies operational but also lays foundation for future innovations highlighting critical factors influence efficiency.

Язык: Английский

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Metal‐Organic‐Cages: Synthetic Strategies and Photocatalytic Application

ChemCatChem, Год журнала: 2024, Номер unknown

Опубликована: Сен. 20, 2024

Abstract Metal‐organic cages (MOCs) are a class of compounds formed through the coordination metal ions with organic ligands to create well‐defined and cage‐like structure. These unique structures offer versatile environments for catalyzing wide range chemical reactions. The catalytic capabilities MOCs significantly influenced by nature ions, functional ligands, cage Notably, confined spaces within can lead enhanced reaction efficiencies, particularly in processes such as light‐induced hydrogen generation photocatalytic reduction CO₂. Furthermore, show great potential photo‐organic synthesis due structure, which provides environment allows encapsulating molecules, making them useful improving selectivity efficiency process. This review reports development photocatalysis, focusing on structural design regulation strategy build production, CO 2 reduction, transformation. Insights into photocatalysis discussed including challenges further research direction MOC‐based photocatalysis.

Язык: Английский

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