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

Or Dishi; Yuval Rahav; Raanan Carmieli; Ori Gidron

doi:10.1002/chem.202202082

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

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

3 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 language	American English
Article number	e202202082
Journal	Chemistry - A European Journal
Volume	28
Issue number	62
DOIs	https://doi.org/10.1002/chem.202202082
State	Published - 7 Nov 2022

Bibliographical note

Funding Information:
This research was supported by the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (Grant Agreement No. 850836, ERC Starting Grant “PolyHelix”). This research was supported by The Israel Science Foundation – FIRST Program (grant No. 1453/19).

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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10.1002/chem.202202082

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

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.",

keywords = "aromaticity, macrocyclic compounds, oligofurans, organic semiconductors, π-conjugated macrocycles",

author = "Or Dishi and Yuval Rahav and Raanan Carmieli and Ori Gidron",

note = "Funding Information: This research was supported by the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (Grant Agreement No. 850836, ERC Starting Grant “PolyHelix”). This research was supported by The Israel Science Foundation – FIRST Program (grant No. 1453/19). Publisher Copyright: {\textcopyright} 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.",

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AU - Rahav, Yuval

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AU - Gidron, Ori

N1 - Funding Information: This research was supported by the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (Grant Agreement No. 850836, ERC Starting Grant “PolyHelix”). This research was supported by The Israel Science Foundation – FIRST Program (grant No. 1453/19). Publisher Copyright: © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

PY - 2022/11/7

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N2 - 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.

AB - 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.

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KW - oligofurans

KW - organic semiconductors

KW - π-conjugated macrocycles

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

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