Journal
NATURE CHEMISTRY
Volume 5, Issue 5, Pages 376-382Publisher
NATURE PUBLISHING GROUP
DOI: 10.1038/nchem.1618
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Funding
- Deutsche Forschungsgemeinschaft (DFG) [NA-686/5]
- Deutsche Akademische Austauschdienst (DAAD)
- Center for Functional Materials and Nanomolecular Science (NanoFun)
- Academy of Finland [127941]
- EPSRC [EP/F035535/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/F035535/1] Funding Source: researchfish
- Academy of Finland (AKA) [127941] Funding Source: Academy of Finland (AKA)
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Inner-phase chemical reactions of guest molecules encapsulated in a macromolecular cavity give fundamental insight into the relative stabilization of transition states by the surrounding walls of the host, thereby modelling the situation of substrates in enzymatic binding pockets. Although in solution several examples of inner-phase reactions are known, the use of cucurbiturils as macrocyclic hosts and bicyclic azoalkanes as guests has now enabled a systematic mass spectrometric investigation of inner-phase reactions in the gas phase, where typically the supply of thermal energy results in dissociation of the supramolecular host-guest assembly. The results reveal a sensitive interplay in which attractive and repulsive van der Waals interactions between the differently sized hosts and guests need to be balanced with a constrictive binding to allow thermally activated chemical reactions to compete with dissociation. The results are important for the understanding of supramolecular reactivity and have implications for catalysis.
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