Application of Hard and Soft Acid‐base Theory to Construct Heterometallic Materials with Metal‐oxo Clusters

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Oct. 24, 2024

Heterometallic cluster-based materials offer the potential to incorporate multiple functionalities, leveraging aggregation effects of clusters and translating this heterogeneity complexity into unexpected properties that are more than just sum their components. However, rational construction heterometallic remains challenging due metal cation coordination structural unpredictability. This minireview provides insights a general synthetic strategy based on Hard Soft Acids Bases (HSAB) theory, summarizing its advantages in designed synthesis discrete (intracluster assembly) infinite (intercluster assembly). Furthermore, it emphasizes exploit intrinsic mixed components achieve breakthroughs across broad range applications. The from review expected drive progress controllable predictable manner.

Language: Английский

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Innovative supramolecular coordination nanomedicine: Targeting inflammation and scavenging ROS for synergistic arthritis therapy

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 160644 - 160644

Published: Feb. 1, 2025

Language: Английский

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Ionic Radius-Dependent Self-Assembly of Lanthanide Organic Polyhedra: Structural Diversities and Luminescent Properties

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

Published: Jan. 1, 2025

This article presents the influence of lanthanide size and ligands conformational flexibility on assemblies their corresponding luminescent properties.

Language: Английский

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Transformation of Zirconium Metal–Organic Cages to Metal–Organic Gels

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

Published: March 11, 2025

Zirconium metal–organic cages (Zr-MOCs) that assemble from zirconocence-based clusters and carboxylate-based ligands have been widely used as building blocks for constructing various MOC-based materials with diverse applications because of their high stability solubilities. However, in this work, we found the structures a series Zr-MOCs are quite flexible when heated at 60 °C an N,N′-dimethylformamide solution, which they completely disassembled into fragments reassembled amorphous gels (MOGs). The transformation mechanism was investigated via proton nuclear magnetic resonance, electrospray ionization mass spectrometry, infrared spectroscopy, X-ray photoelectron other techniques, revealed cyclopentadiene (CP) breaks out [Zr3CP3(μ2-OH)3(μ3-O)] cluster remains whereas trinuclear [Zr3(μ2-OH)3(μ3-O)] dimerizes hexanuclear [Zr6(μ2-OH)6(μ3-O)2] forms MOGs terephthalic acid-based ligands. reported based on different substituent groups, longer biphenyl dicarboxylic acids, trimesic acids all undergo such MOC-to-MOG transformations, indicating good versatility transformation. In addition, posttreatment appropriate amount acetic acid could regulate crystallinity MOGs, thus giving rise to containing nano-UiO-66-type MOF crystals xerogels improved porosity.

Language: Английский

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Asymmetric Cascade Photocycloaddition-Acyloin Rearrangement Enabled by Cage-Confined Visible-Light Catalysis

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

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Application of Hard and Soft Acid‐base Theory to Construct Heterometallic Materials with Metal‐oxo Clusters

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Oct. 24, 2024

Abstract Heterometallic cluster‐based materials offer the potential to incorporate multiple functionalities, leveraging aggregation effects of clusters and translating this heterogeneity complexity into unexpected properties that are more than just sum their components. However, rational construction heterometallic remains challenging due metal cation coordination structural unpredictability. This minireview provides insights a general synthetic strategy based on Hard Soft Acids Bases (HSAB) theory, summarizing its advantages in designed synthesis discrete (intracluster assembly) infinite (intercluster assembly). Furthermore, it emphasizes exploit intrinsic mixed components achieve breakthroughs across broad range applications. The from review expected drive progress controllable predictable manner.

Language: Английский

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