We report the construction of frustrated Lewis pairs (FLPs) in a metal-organic framework (MOF), where both Lewis acid (LA) and Lewis base (LB) are fixed to the backbone. The anchoring of a tritopic organoboron linker as LA and a monotopic linker as LB to separate metal oxide clusters in a tetrahedron geometry allows for the precise control of distance between them. As the type of monotopic LB linker varies, pyridine, phenol, aniline, and benzyl alcohol, a series of 11 FLPs were constructed to give fixed distances of 7.1, 5.5, 5.4, and 4.8 Å, respectively, revealed by B-H solid-state nuclear magnetic resonance spectroscopy. Keeping LA and LB apart by a fixed distance makes it possible to investigate the electrostatic effect by changing the functional groups in the monotopic LB linker, while the LA counterpart remains unaffected. This approach offers new chemical environments of the active site for FLP-induced catalysis.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/jacs.4c03133 | DOI Listing |
J Am Chem Soc
May 2024
Key Laboratory of Biomedical Polymers Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
We report the construction of frustrated Lewis pairs (FLPs) in a metal-organic framework (MOF), where both Lewis acid (LA) and Lewis base (LB) are fixed to the backbone. The anchoring of a tritopic organoboron linker as LA and a monotopic linker as LB to separate metal oxide clusters in a tetrahedron geometry allows for the precise control of distance between them. As the type of monotopic LB linker varies, pyridine, phenol, aniline, and benzyl alcohol, a series of 11 FLPs were constructed to give fixed distances of 7.
View Article and Find Full Text PDFACS Cent Sci
January 2024
Molecular Foundry Lawrence Berkeley National Laboratory 1 Cyclotron Road, Berkeley, California 94270, United States.
Elastomers are widely used in textiles, foam, and rubber, yet they are rarely recycled due to the difficulty in deconstructing polymer chains to reusable monomers. Introducing reversible bonds in these materials offers prospects for improving their circularity; however, concomitant bond exchange permits creep, which is undesirable. Here, we show how to architect dynamic covalent polydiketoenamine (PDK) elastomers prepared from polyetheramine and triketone monomers, not only for energy-efficient circularity, but also for outstanding creep resistance at high temperature.
View Article and Find Full Text PDFMolecules
December 2022
National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia.
One of the biggest advantages of MOFs is the possibility of modifying their properties and tuning their inherent activity (i.e., sorption, storage, catalytic activity etc.
View Article and Find Full Text PDFJ Comput Aided Mol Des
February 2021
Department of Biochemistry and Biomedicine, School of Life Sciences, University of Sussex, Falmer, Brighton, BN1 9QG, UK.
The alternative oxidase (AOX) is a monotopic diiron carboxylate protein that catalyses the oxidation of ubiquinol and the reduction of oxygen to water. Although a number of AOX inhibitors have been discovered, little is still known about the ligand-protein interaction and essential chemical characteristics of compounds required for a potent inhibition. Furthermore, owing to the rapidly growing resistance to existing inhibitors, new compounds with improved potency and pharmacokinetic properties are urgently required.
View Article and Find Full Text PDFJ Am Chem Soc
September 2020
Key Laboratory of Biomedical Polymers, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
We report the construction of a molecular vise by pairing a tritopic phenylphosphorus(III) linker and a monotopic linker in opposite positions within a metal-organic framework. The angle between these linkers at metal sites is fixed upon changing the functionality in the monotopic linker, while the distance between them is precisely tuned. This distance within the molecular vise is accurately measured by H-P solid-state nuclear magnetic resonance spectroscopy.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!