Exploring the Gas-Phase Formation and Chemical Reactivity of Highly Reduced M 8 L 6 Coordination Cages.

Autor: Pfrunder MC; Centre for Materials Science (CFMS), Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland, 4000, Australia.; School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, Queensland, 4000, Australia., Marshall DL; Centre for Materials Science (CFMS), Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland, 4000, Australia.; Central Analytical Research Facility (CARF), Queensland University of Technology, 2 George Street, Brisbane, Queensland, 4000, Australia., Poad BLJ; Centre for Materials Science (CFMS), Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland, 4000, Australia.; School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, Queensland, 4000, Australia.; Central Analytical Research Facility (CARF), Queensland University of Technology, 2 George Street, Brisbane, Queensland, 4000, Australia., Stovell EG; School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, Queensland, 4000, Australia., Loomans BI; Centre for Materials Science (CFMS), Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland, 4000, Australia.; School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, Queensland, 4000, Australia., Blinco JP; Centre for Materials Science (CFMS), Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland, 4000, Australia.; School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, Queensland, 4000, Australia., Blanksby SJ; Centre for Materials Science (CFMS), Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland, 4000, Australia.; School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, Queensland, 4000, Australia.; Central Analytical Research Facility (CARF), Queensland University of Technology, 2 George Street, Brisbane, Queensland, 4000, Australia., McMurtrie JC; Centre for Materials Science (CFMS), Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland, 4000, Australia.; School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, Queensland, 4000, Australia., Mullen KM; Centre for Materials Science (CFMS), Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland, 4000, Australia.; School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, Queensland, 4000, Australia.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2022 Nov 07; Vol. 61 (45), pp. e202212710. Date of Electronic Publication: 2022 Oct 07.
DOI: 10.1002/anie.202212710
Abstrakt: Coordination cages with well-defined cavities show great promise in the field of catalysis on account of their unique combination of molecular confinement effects and transition-metal redox chemistry. Here, three coordination cages are reduced from their native 16 + oxidation state to the 2 + state in the gas phase without observable structural degradation. Using this method, the reaction rate constants for each reduction step were determined, with no noticeable differences arising following either the incorporation of a C 60 -fullerene guest or alteration of the cage chemical structure. The reactivity of highly reduced cage species toward molecular oxygen is "switched-on" after a threshold number of reduction steps, which is influenced by guest molecules and the structure of cage components. These new experimental approaches provide a unique window to explore the chemistry of highly-reduced cage species that can be modulated by altering their structures and encapsulated guest species.
(© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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