Molecular Vises for Precisely Positioning Ligands near Catalytic Metal Centers in Metal–Organic Frameworks

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 th...

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Published inJournal of the American Chemical Society Vol. 142; no. 38; pp. 16182 - 16187
Main Authors Yan, Wei, Li, Shenhui, Yang, Tao, Xia, Yucong, Zhang, Xinrui, Wang, Chao, Yan, Zier, Deng, Feng, Zhou, Qianghui, Deng, Hexiang
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 23.09.2020
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Abstract 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 1H–31P solid-state nuclear magnetic resonance spectroscopy. This unveils the impact of the distance on catalytic performance without interference from electrostatic effects or changes in the angle of the ligand, which is unprecedented in classic organometallic complexes.
AbstractList 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. This unveils the impact of the distance on catalytic performance without interference from electrostatic effects or changes in the angle of the ligand, which is unprecedented in classic organometallic complexes.
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 1H–31P solid-state nuclear magnetic resonance spectroscopy. This unveils the impact of the distance on catalytic performance without interference from electrostatic effects or changes in the angle of the ligand, which is unprecedented in classic organometallic complexes.
Author Li, Shenhui
Xia, Yucong
Zhang, Xinrui
Yang, Tao
Wang, Chao
Yan, Wei
Deng, Feng
Yan, Zier
Deng, Hexiang
Zhou, Qianghui
AuthorAffiliation The Institute for Advanced Studies
Chinese Academy of Sciences
State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology
Key Laboratory of Biomedical Polymers, Ministry of Education, College of Chemistry and Molecular Sciences
Sauvage Center for Molecular Sciences, Engineering Research Center of Organosilicon Compounds & Materials (Ministry of Education), College of Chemistry and Molecular Sciences
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Snippet We report the construction of a molecular vise by pairing a tritopic phenyl­phosphorus­(III) linker and a monotopic linker in opposite positions within a...
We report the construction of a molecular vise by pairing a tritopic phenylphosphorus(III) linker and a monotopic linker in opposite positions within a...
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Title Molecular Vises for Precisely Positioning Ligands near Catalytic Metal Centers in Metal–Organic Frameworks
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