Cation induced changes to the structure of cryptophane cages.

Autor: Lloyd Williams OH; School of Chemistry, UNSW Sydney, Sydney, NSW, 2052, Australia. n.rijs@unsw.edu.au., Cox CS; School of Chemistry, UNSW Sydney, Sydney, NSW, 2052, Australia. n.rijs@unsw.edu.au., Zhang MY; School of Chemistry, UNSW Sydney, Sydney, NSW, 2052, Australia. n.rijs@unsw.edu.au., Lessio M; School of Chemistry, UNSW Sydney, Sydney, NSW, 2052, Australia. n.rijs@unsw.edu.au., Rusli O; School of Chemistry, UNSW Sydney, Sydney, NSW, 2052, Australia. n.rijs@unsw.edu.au., Donald WA; School of Chemistry, UNSW Sydney, Sydney, NSW, 2052, Australia. n.rijs@unsw.edu.au., Jekimovs L; School of Chemistry and Physics, Queensland University of Technology, Brisbane 4001, Queensland, Australia., Marshall DL; Central Analytical Research Facility, Queensland University of Technology, Brisbane, 4001 Australia., Pfrunder MC; School of Chemistry and Physics, Queensland University of Technology, Brisbane 4001, Queensland, Australia.; Centre for Materials Science, Queensland University of Technology, Brisbane, 4001 Australia., Poad BLJ; School of Chemistry and Physics, Queensland University of Technology, Brisbane 4001, Queensland, Australia.; Central Analytical Research Facility, Queensland University of Technology, Brisbane, 4001 Australia., Brotin T; ENS Lyon, CNRS, Laboratoire de Chimie, UMR 5182, 46 Allée d'Italie, 69364 Lyon, France., Rijs NJ; School of Chemistry, UNSW Sydney, Sydney, NSW, 2052, Australia. n.rijs@unsw.edu.au.
Jazyk: angličtina
Zdroj: Dalton transactions (Cambridge, England : 2003) [Dalton Trans] 2024 Nov 26; Vol. 53 (46), pp. 18473-18483. Date of Electronic Publication: 2024 Nov 26.
DOI: 10.1039/d4dt01824a
Abstrakt: Here the monocation complexes of seven anti -cryptophanes are examined with high-resolution ion-mobility mass spectrometry. The relative size of the [cation + cryptophane] + complexes were compared based on their measured mobilities and derived collisional cross sections. A paradoxical trend of structural contraction was observed for complexes of increasing cation size. Density functional theory confirmed encapsulation occurs for cation = Na + , K + , Rb + , Cs + and NH 4 + . However, cation = Li + preferred oxygen coordination at a linker over encapsulation within the cavity, leading to a slightly larger gas phase structure overall. Protonated cryptophanes yielded much larger collision cross sections via imploded cryptophane structures. Thus, competing physical effects led to the observed non-periodic size trend of the complexes. Trends in complexation from isothermal titration calorimetry and other condensed phase techniques were borne out by the gas phase studies. Further, predicted cavity sizes compared with the gas phase experimental findings reveal more about the encapsulation mechanisms themselves.
Databáze: MEDLINE
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