Functionalisation of conjugated macrocycles with type I and II concealed antiaromaticity via cross-coupling reactions

Troy L.R. Bennett, Adam V. Marsh, James M. Turner, Felix Plasser, Martin Heeney, Florian Glöcklhofer*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Scopus citations


Conjugated macrocycles can exhibit concealed antiaromaticity; that is, despite not being antiaromatic, under specific circumstances, they can display properties typically observed in antiaromatic molecules due to their formal macrocyclic 4n π-electron system. Paracyclophanetetraene (PCT) and its derivatives are prime examples of macrocycles exhibiting this behaviour. In redox reactions and upon photoexcitation, they have been shown to behave like antiaromatic molecules (requiring type I and II concealed antiaromaticity, respectively), with such phenomena showing potential for use in battery electrode materials and other electronic applications. However, further exploration of PCTs has been hindered by the lack of halogenated molecular building blocks that would permit their integration into larger conjugated molecules by cross-coupling reactions. Here, we present two dibrominated PCTs, obtained as a mixture of regioisomers from a three-step synthesis, and demonstrate their functionalisation via Suzuki cross-coupling reactions. Optical, electrochemical, and theoretical studies reveal that aryl substituents can subtly tune the properties and behaviour of PCT, showing that this is a viable strategy in further exploring this promising class of materials.

Original languageEnglish (US)
Pages (from-to)713-720
Number of pages8
JournalMolecular Systems Design and Engineering
Issue number6
StatePublished - May 10 2023

Bibliographical note

Publisher Copyright:
© 2023 The Royal Society of Chemistry.

ASJC Scopus subject areas

  • Chemistry (miscellaneous)
  • Chemical Engineering (miscellaneous)
  • Biomedical Engineering
  • Energy Engineering and Power Technology
  • Process Chemistry and Technology
  • Industrial and Manufacturing Engineering
  • Materials Chemistry


Dive into the research topics of 'Functionalisation of conjugated macrocycles with type I and II concealed antiaromaticity via cross-coupling reactions'. Together they form a unique fingerprint.

Cite this