Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 22, Issue 43, Pages 15231-15236Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201603596
Keywords
arenes; encapsulation; keplerates; NMR spectroscopy; polyoxometalate
Categories
Funding
- Israel Science Foundation [763/14]
- Helen and Martin Kimmel Center for Molecular Design
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The use of confined space to modulate chemical reactivity and to sequester organic compounds spans significant disciplines in chemistry and biology. Here, the inclusion and assembly of arenes into a water-soluble porous metal oxide nanocapsule [{(Mo-VI)(Mo5O21)-O-V(H2O)(6)}(12){(Mo2O4)-O-V(CH3COO)}(30)](42-) (Mo-132) is reported. The uptake of benzene, halobenzenes, alkylbenzenes, phenols, and other derivatives was studied by NMR, where it was possible to follow the encapsulation process from the outside of the capsule through its pores and then into the interior. The importance of size or shape of the arenes, and various intermolecular bond interactions contributed by the benzene substituent on the encapsulation process was studied, showing the importance of pi-pi stacking and CH-pi interactions. Furthermore, by using NOESY, ROESY, and HOESY NMR techniques it was possible to understand the interaction of the encapsulated arenes and the acetate linkers or ligands that line the interior of the Mo-132 capsule.
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