Carbon Dioxide Fixation and Sulfate Sequestration by a Supramolecular Trigonal Bipyramid. (31st July 2015)

• Record Type: Journal Article
• Authors: Browne, Colm; Ramsay, William J.; Ronson, Tanya K.; Medley‐Hallam, John; Nitschke, Jonathan R.
• Is Part Of: Angewandte Chemie. Volume 127:Number 38(2015)
• Page Start: 11274
• Page End: 11279
• Publication Date: 2015-07-31
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201504856
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The subcomponent self‐assembly of a bent dialdehyde ligand and different cationic and anionic templates led to the formation of two new metallosupramolecular architectures: a Fe^II₄L₆ molecular rectangle was isolated following reaction of the ligand with iron(II) tetrafluoroborate, and a M₅L₆ trigonal bipyramidal structure was constructed from either zinc(II) tetrafluoroborate or cadmium(II) trifluoromethanesulfonate. The spatially constrained arrangement of the three equatorial metal ions in the M₅L₆ structures was found to induce small‐molecule transformations. Atmospheric carbon dioxide was fixed as carbonate and bound to the equatorial metal centers in both the Zn₅L₆ and Cd₅L₆ assemblies, and sulfur dioxide was hydrated and bound as the sulfite dianion in the Zn₅L₆ structure. Subsequent in situ oxidation of the sulfite dianion resulted in a sulfate dianion bound within the supramolecular pocket.</p> </abstract>