A Macrocyclic Furan with Accessible Oxidation States: Switching Between Aromatic and Antiaromatic Global Ring Currents

Or Dishi, Yuval Rahav, Raanan Carmieli, Ori Gidron*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

Macrocyclic furans are predicted to switch between global aromaticity and antiaromaticity, depending on their oxidation states. However, the macrocyclic furans reported to date are stabilized by electron withdrawing groups, which result in inaccessible oxidation states. To circumvent this problem, a post-macrocyclization approach was applied to introduce methylene-substituted macrocyclic furans, which display an extremely low oxidation potential of −0.23 vs. Fc/Fc+, and are partially oxidized in ambient conditions. Additional oxidation to the dication results in aromaticity switching to a global 30πe aromatic state, as indicated by the formation of a strong diatropic current observed in the 1H NMR spectrum. NICS and ACID calculations support this trend and provide evidence for a different pathway for the global current in the neutral and dicationic states. According to these findings, macrocyclic furans can be rendered as promising p-type materials with stable oxidation states.

Original languageAmerican English
Article numbere202202082
JournalChemistry - A European Journal
Volume28
Issue number62
DOIs
StatePublished - 7 Nov 2022

Bibliographical note

Publisher Copyright:
© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

Keywords

  • aromaticity
  • macrocyclic compounds
  • oligofurans
  • organic semiconductors
  • π-conjugated macrocycles

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