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Carbon Dioxide Fixation and Sulfate Sequestration by a Supramolecular Trigonal Bipyramid
Author(s) -
Browne Colm,
Ramsay William J.,
Ronson Tanya K.,
MedleyHallam John,
Nitschke Jonathan R.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201504856
Subject(s) - chemistry , trigonal bipyramidal molecular geometry , inorganic chemistry , sulfite , cationic polymerization , crystallography , polymer chemistry , crystal structure
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 II 4 L 6 molecular rectangle was isolated following reaction of the ligand with iron(II) tetrafluoroborate, and a M 5 L 6 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 M 5 L 6 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 Zn 5 L 6 and Cd 5 L 6 assemblies, and sulfur dioxide was hydrated and bound as the sulfite dianion in the Zn 5 L 6 structure. Subsequent in situ oxidation of the sulfite dianion resulted in a sulfate dianion bound within the supramolecular pocket.