Construction of a Lanthanide Cage with a Hollow-Walled Cavity and Large Windows to Promote Nucleophilic Additions DOI
Jingzhe Li,

Fan Dong,

Manchang Kou

et al.

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(21), P. 10699 - 10709

Published: Oct. 28, 2024

Metal–organic cages (MOCs) as artificial mimic enzymes can allow small organic molecules to freely move in and out of the cavity with confined space, which often increase intermolecular collisions accelerate those reactions that are difficult occur. This kind homogeneous catalyst possesses high catalytic activity regioselectivity, attracting growing interest recently. However, rational design MOCs large openings well rich active sites for efficient chemical conversions remains a great challenge. Herein, we report decanuclear 3d-4f MOC, Zn2Yb8, hollow-walled four windows self-assembled cooperatively by bridging ligands, Zn-based metalloligands, lanthanide Yb3+ ions. The lantern-like Zn2Yb8 not only exposes unblocked passageways allowing more guest penetrate cage smoothly but also provides Lewis centers within cavity, could promote nucleophilic additions effectively boost Friedel–Crafts alkylation three-component Strecker reaction. With catalyst, than 13 bis(indolyl)methane derivatives be synthesized easily 53–98% through alkylation, conversion reaction aniline, benzaldehyde, trimethylsilyl cyanide achieve approximately 98% 3 h. Furthermore, host–guest relationship investigations confirmed function mainly attributed synergy inherent confinement effect, multiple sites, electrostatic interactions coordination cage. construction discrete MOC its applications may represent potential approach developing enzyme-like supramolecular nanoreactors.

Language: Английский

Multicomponent, Multicavity Metallacages That Contain Different Binding Sites for Allosteric Recognition DOI
Haifei Liu, Chenxing Guo, Luqi Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 15787 - 15795

Published: May 13, 2024

The encapsulation of different guest molecules by their recognition domains proteins leads to selective binding, catalysis, and transportation. Synthetic hosts capable selectively binding guests in cavities mimic the function are highly desirable but challenging. Here, we report three ladder-shaped, triple-cavity metallacages prepared multicomponent coordination-driven self-assembly. Interestingly, porphyrin-based metallacage is heteroleptic fullerenes (C60 or C70) coronene using its cavities, allowing distinct allosteric upon addition C60 C70. Owing affinities one molecule central cavity two units side while encapsulating C70 cavity. rational design multicavity assemblies that enable will guide further advanced supramolecular constructs with tunable properties.

Language: Английский

Citations

13
Selective heterogeneous photocatalytic activation for toluene oxidation: recent advances, challenges and perspective DOI Open Access
Shiqin Gao, Li Bai, Tao Gan

et al.

Chemical Synthesis, Journal Year: 2025, Volume and Issue: 5(1)

Published: Feb. 8, 2025

The conversion of toluene into high-value products without generating undesired CO2 remains a critical challenge. Selective oxidation under visible light irradiation has emerged as promising solution. This review offers comprehensive interpretation photocatalytic transformations in heterogeneous oxidation. We start by outlining the basic mechanism C–H bond activation and provide an overview reactive oxygen species (ROS) within systems. Subsequently, we summary strategies that have been developed to enhance selectivity system. Following this, advanced characterization techniques density functional theory (DFT) calculations are discussed for understanding structure-performance relationship photocatalysts mechanisms underlying processes. Finally, put forward detailed discussion current challenges potential directions future research, with aim offering valuable insights this emerging field. believe will not only spark greater creativity optimizing but also offer designing other

Language: Английский

Citations

1
Low-Voltage Electrooxidation of Benzyl Alcohol to Benzoic Acid Enhanced by PtZn-ZnOx Interface DOI

Renfeng Liu,

Wenjing Tu,

An Pei

et al.

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

Published: March 11, 2025

The electrocatalytic oxidation of benzyl alcohol to benzoic acid is a process that often requires high voltage, leading increased energy consumption, side reactions (oxygen evolution reaction (OER)), and catalyst degradation. Herein, our study introduces novel approach. We demonstrate PtZn-ZnOx featuring PtZn intermetallic structure with abundant interfaces on the surface allows for an impressive selectivity 99.5% at low potential 0.725 V (vs reversible hydrogen electrode, RHE), which 0.6 lower than most reported studies. This testament efficiency catalyst, as it significantly reduces occurrence reactions, more efficient sustainable process. experimental density functional theory calculations demonstrated adsorption Ph–CH2OH Ph–CHO generation electrophilic OH* were promoted due unsaturated coordination Zn atom in interfaces. Furthermore, potential-determining step coupling was barrier interface, improved catalytic activity selectivity. outlines approach designing highly electrocatalysts high-efficiency valorization voltages.

Language: Английский

Citations

1
Confining polyoxometalates in porphyrin-based porous cationic polymer toward boosting visible-light-driven synthesis of sulfoxides and detoxification of mustard gas simulants DOI
Qingshan Zhu, Haiyan An,

Yuting Wei

et al.

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 436, P. 115627 - 115627

Published: July 1, 2024

Language: Английский

Citations

6
Sustainable scalable solid-state synthesis of highly efficient synergetic 2D/0D micro/nanostructured g-C3N4/CdS photocatalysts for hydrogen production and water purification DOI
Natalya Khan, Gairat Burashev,

Ayaulym Kadylbekova

et al.

Sustainable materials and technologies, Journal Year: 2024, Volume and Issue: 41, P. e01063 - e01063

Published: July 27, 2024

Language: Английский

Citations

5
Metal‐Organic Frameworks (MOFs) and Metal‐Organic Cages (MOCs) for Photocatalytic Hydrogen Production DOI
Chaoqun Mu,

Shijin Jian,

Mingming Zhang

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(43)

Published: May 29, 2024

Abstract Metal‐organic frameworks (MOFs) and metal‐organic cages (MOCs) have garnered significant attention as promising photocatalysts due to their tunable chemical structures integrated multifunctionality. To increase the photocatalytic efficiency, strategies like ligand functionalization, introducing additional catalytic sites, doping or encapsulating photosensitizers been explored for both MOFs MOCs. This concept review focuses on recent advancements in utilizing MOCs hydrogen production, highlighting unique characteristics respective mechanisms this field. Moreover, it outlines current challenges prospects faced by MOCs, offering an outlook future domain.

Language: Английский

Citations

4
Tetraphenylethene-Based Molecular Cage with Coenzyme FAD: Conformationally Isomeric Complexation toward Photocatalysis-Assisted Photodynamic Therapy DOI
Qingfang Li, Chaochao Yan, Peijuan Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(45), P. 30933 - 30946

Published: Oct. 21, 2024

Flavin adenine dinucleotide (FAD), serving as a light-absorbing coenzyme factor, can undergo conformationally isomeric complexation within different enzymes to form various enzyme-coenzyme complexes, which exhibit photocatalytic functions that play crucial role in physiological processes. Constructing an artificial photofunctional system using FAD or its derivatives not only develop biocompatible systems with excellent activities but also further enhance our understanding of the biological systems. Here, we demonstrate supramolecular approach for constructing enzyme-coenzyme-type host-guest complex photoinduced catalytic function water. First, have designed and synthesized water-soluble tetraphenylethene (TPE)-based octacationic molecular cage (

Language: Английский

Citations

4
Chemo-Selective Transformation of Anthracene Derivative within Water-Soluble Coordination Cages Having Different Cavities DOI
Valiyakath Abdul Rinshad,

Shamsad Ali,

Neal Hickey

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 12, 2025

Coordination cages with specific properties and functionalities are utilized as reaction vessels for the desired chemical transformation of substrates. The symmetry inherent cavity coordination can influence host–guest interactions outcome in their confined space. However, impact cage shape on different transformations remains unclear. In this chapter, we report chemo-selective anthracene derivative using three geometrically distinct Pd6 (CC2, CC3, CC4). Photoirradiation 9-bromoanthracene (G3) distorted double-square (CC2) yields anthracene-9,10-dione, while known (CC3) forms a [4 + 4] cycloaddition product. same bowl-shaped (CC4) resulted oxidized Through combination experimental computational studies, demonstrate that size significantly pathways encapsulated derivative, leading to chemo-selectivity. Furthermore, observe encapsulation cavities (CC2 CC4) leads significant enhancement rate photooxidation G3. This work underscores versatility water-soluble synthetic chemistry, offering interesting avenues transformation.

Language: Английский

Citations

0
Supramolecular Light-Emitting Materials Based on Multicomponent Metallacages DOI
Chaoqun Mu, Mingming Zhang

Published: Jan. 1, 2025

Language: Английский

Citations

0
Multicomponent Metallacages via the Integrative Self-Assembly of Pt(II) Nodes with Multiple Pyridyl and Carboxylate Ligands DOI

Yali Hou,

Zeyuan Zhang,

Mingming Zhang

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: May 2, 2025

ConspectusIn recent years, multicomponent self-assembly has emerged as a pivotal strategy in supramolecular chemistry, enabling the construction of artificial systems with enhanced functionalities that surpass those individual molecular components. These assemblies have garnered significant interest due to their potential applications recognition, catalysis, and biomedical engineering. However, achieving precise control over assembly process remains challenge, increased structural complexity often results thermodynamic mixtures, limiting practical applications. In this context, metal-coordination-driven promising strategy, moderate strength good directionality metal-ligand bonds ensure formation discrete architectures well-defined structures geometries. Notably, integration pyridyl carboxylate donors cis-Pt(II) nodes offers an effective approach for constructing metallacages. This method is particularly attractive its ability enable heteroleptic assembly, along accessibility tunability ligands, which impart desirable photophysical properties anticancer activities.This Account provides comprehensive overview our work on design, preparation, functionalization metallacages via ligands nodes. By strategically tailoring ligand adjusting number coordination sites, we successfully constructed diverse geometries, including tetragonal hexagonal prisms, triple-cavity ladders, truncated octahedra, cyclic bis[2]catenanes, etc. particular, highlight use functional such tetraphenylethylene, hexaphenylbenzene, perylene diimide, porphyrin derivatives, explore these Tetraphenylethylene hexaphenylbenzene derivatives are propeller-shaped molecules aggregation-induced emission properties, enhancing both solution solid state. Perylene diimide electron-deficient, planar conjugated structures, contribute strong solution, thereby improving host-guest chemistry luminescent Porphyrin owing excellent photosensitivity, endow photocatalytic capabilities. Additionally, other phenanthroline triazine been employed antibacterial SO2 adsorption respectively, Furthermore, metallacage-cross-linked networks exhibit mechanical superior processability, making them candidates materials. At conclusion Account, address challenges future perspectives development We believe ongoing research field will significantly advance understanding metal-coordination

Language: Английский

Citations

0