Steric Repulsion Induced Conformational Switch in Supramolecular Structures
Citation:
Norvaiša, Karolis, Maguire, Sophie, Donohoe, Claire, O'Brien, John E., Twamley, Brendan, Gomes-da-Silva, Ligia C., Senge, Mathias O., Steric Repulsion Induced Conformational Switch in Supramolecular Structures, Chemistry - A European Journal, 2022, 28, 4Download Item:
Abstract:
Inspired by the rigidified architecture of ‘picket-fence’ systems, we propose a strategy utilizing strain to impose intramolecular tension in already peripherally overcrowded structures leading to selective atropisomeric conversion. Employing this approach, tuneable shape-persistent porphyrin conformations were acquired exhibiting distinctive supramolecular nanostructures based on the orientation of the peripheral groups. The intrinsic assemblies driven by non-covalent bonding interactions form supramolecular polymers while encapsulating small molecules in parallel channels or solvent-accessible voids. The developed molecular strain engineering methodologies combined with synthetic approaches have allowed the introduction of the pivalate units creating a highly strained molecular skeleton. Changes in the absorption spectrum indicated the presence of severe steric repulsions between the peripheral groups which were confirmed by single crystal X-ray analysis. To release the steric strain introduced by the peripheral units, thermal equilibration strategies were used to selectively convert the most abundant atropisomer to the desirable minor one.
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http://people.tcd.ie/sengem
Author: Senge, Mathias
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Chemistry - A European Journal;28;
4;
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http://dx.doi.org/10.1002/chem.202103879Metadata
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