Lookup NU author(s): Emeritus Professor Bill Clegg
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A family of push-pull quinoidal porphyrin monomers has been prepared from a meso-formyl porphyrin by bromination,thioacetal formation, palladium-catalyzed coupling with malononitrile and oxidation with DDQ. Attempts at extending thissynthesis to a push-pull quinoidal/cumulenic porphyrin dimer were not successful. The crystal structures of the quinoidalporphyrins indicate that there is no significant contribution from singlet biradical or zwitterionic resonance forms. Thecrystal structure of an ethyne-linked porphyrin dimer shows that the torsion angle between the porphyrin units is onlyabout 3°, in keeping with crystallographic results on related compounds, but contrasting with the torsion angle of about35° predicted by computational studies. The free-base quinoidal porphyrin monomers form tightly π-stacked layerstructures, despite their curved geometries and bulky aryl substituents.
Author(s): Smith MJ, Blake IM, Clegg W, Anderson HL
Publication type: Article
Publication status: Published
Journal: Organic and Biomolecular Chemistry
Print publication date: 21/05/2018
Online publication date: 24/04/2018
Acceptance date: 24/04/2018
ISSN (print): 1477-0520
ISSN (electronic): 1477-0539
Publisher: Royal Society of Chemistry
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