AI Article Synopsis
- The study discusses the successful isolation of vanadium(II) in a metal-organic framework (MOF) using a specific reaction involving vanadium(III) and a compound with silyl groups.
- The resulting material features a unique secondary building unit with open coordination sites that can react with oxygen to form vanadium-superoxo species.
- This process not only improves the adsorption properties for methane but also offers a new method to create low-valent metal sites in MOFs, which can lead to new intermediate species without losing the framework's stability.
Article Abstract
We report the isolation of vanadium(II) in a metal-organic framework (MOF) by the reaction of the chloride-capped secondary building unit in the all-vanadium(III) V-MIL-101 () with 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine. The reduced material, , has a secondary building unit with the formal composition [VV], with each metal ion presenting one open coordination site. Subsequent reaction with O yields a side-on η vanadium-superoxo species, . The MOF featuring V(III)-superoxo moieties exhibits a mild enhancement in the isosteric enthalpy of adsorption for methane compared to the parent V-MIL-101. We present this synthetic methodology as a potentially broad way to access low-valent open metal sites within MOFs without causing a loss of crystallinity or porosity. The low-valent sites can serve as isolable intermediates to access species otherwise inaccessible by direct synthesis.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.inorgchem.1c02850 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Homochiral BINOL-Based Metal-Organic Frameworks for Luminescence Sensing of Hydrobenzoin Enantiomers.
Inorg Chem
January 2025
Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States.
Luminescent chiral metal-organic frameworks (CMOFs) are promising candidates for the enantioselective sensing of important chiral molecules. Herein, we report the synthesis and characterization of Zn and Cd CMOFs based on 1,1'-bi-2-naphthol (BINOL)-derived 3,3',6,6'-tetra(benzoic acids), H-OEt and H-OH. Four CMOFs, -OEt, -OH, -OEt, and -OH, based on these ligands were crystallographically characterized.
View Article and Find Full Text PDFTailoring molecular diffusion in core-shell zeolite imidazolate framework composites realizes efficient kinetic separation of xylene isomers.
Angew Chem Int Ed Engl
January 2025
Zhejiang University, Key Laboratory of Biomass Chemical Engineering of the Ministry of Education, College of Chemical and Biological Engineering, 866 Yuhangtang Road, Xihu District, hangzhou City, 310058, Hangzhou, CHINA.
The separation of xylene isomers is a critical and energy-intensive process in the petrochemical industry, primarily due to their closely similar molecular structures and boiling points. In this work, we report the synthesis and application of a novel core-shell zeolitic imidazolate framework (ZIF) composite, ZIF-65@ZIF-67, designed to significantly enhance the kinetic separation of xylene isomers through a synergistic "shell-gated diffusion and core-facilitated transport" strategy. The external ZIF-67 shell selectively restricts the diffusion of larger isomers (MX and OX), while the internal ZIF-65 core accelerates the diffusion of PX, thereby amplifying the diffusion differences among the isomers.
View Article and Find Full Text PDFMolecular Mechanism Behind the Capture of Fluorinated Gases by Metal-Organic Frameworks.
Nanomicro Lett
January 2025
College of Environmental Science and Engineering, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Siping Rd 1239, Shanghai, 200092, People's Republic of China.
Fluorinated gases (F-gases) play a vital role in the chemical industry and in the fields of air conditioning, refrigeration, health care, and organic synthesis. However, the direct emission of waste gases containing F-gases into the atmosphere contributes to greenhouse effects and generates toxic substances. Developing porous materials for the energy-efficient capture, separation, and recovery of F-gases is highly desired.
View Article and Find Full Text PDFKirkendall Effect-Mediated Transformation of ZIF-67 to NiCo-LDH Nanocages as Oxidase Mimics for Multicolor Point-of-Care Testing of β-Galactosidase Activity and .
Anal Chem
January 2025
Yunnan Key Laboratory of Modern Separation Analysis and Substance Transformation, College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, Yunnan Province, P. R. China.
Early and portable detection of pathogenic bacteria is crucial for ensuring food safety, monitoring product quality, and tracing the sources of bacterial infections. Moving beyond traditional plate-culture counting methods, the analysis of active bacterial components offers a rapid means of quantifying bacteria. Here, metal-organic framework (MOF)-derived NiCo-layered double hydroxide nanosheets (LDHs), synthesized via the Kirkendall effect, were employed as highly effective oxidase mimics to generate reactive oxygen species (ROS).
View Article and Find Full Text PDFSimultaneous pore confinement and sidewall modification of an N-rich COF with Pd(II): an efficient and sustainable heterogeneous catalyst for cross-coupling reactions.
Nanoscale
January 2025
Department of Chemistry, Indian Institute of Technology Patna, Patna 801106, Bihar, India.
Covalent organic frameworks (COFs) are crystalline porous materials bearing well-ordered two- or three-dimensional molecular tectons in their polymeric skeletal framework. COFs are structurally robust as well as physiochemically stable. Currently, these are being developed for their use as "heterogeneous catalysts" for various organic transformations.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!