Supramolecular Umpolung via Esterification: Converting Electron-Rich Phenolic Macrocycles into CH-Bonding Anion Receptors and Transporters
- 1Institute of Organic Chemistry Polish Academy of Sciences , , Kasprzaka 44/52 , ,
- 2University of Warsaw , , Żwirki i Wigury 101 , ,
- 3Nicolaus Copernicus University in Toruń , , Gagarina 7 , ,
Abstract
CH-bonding anion receptors are supramolecular hosts that combine high chemical robustness, reduced propensity for deprotonation, and distinctive selectivity patterns, which make them attractive for transmembrane transport and medicinal applications. Their broader use is, however, limited by the scarcity of scaffolds capable of forming strong CH···anion interactions. Here, we present a general and operationally simple “supramolecular umpolung” strategy that converts π-electron-rich oligophenolic macrocycles into CH-bonding anion receptors and transporters via esterification of their OH groups. Resorcinarenes and pyrogallolarenes were transformed into acetyl (−OAc), triflate (−OTf), and pentafluorobenzenesulfonate (−OPFB) esters. The −OTf and −OPFB derivatives show high anion binding affinities across diverse media, while −OTf derivatives also act as excellent anion transporters in lipid bilayers, outperforming benchmark tetranitroresorcinarene. Per-triflated pyrogallolarene combines high chloride affinity (Ka ≈ 1010 M–1 in THF), outstanding Cl–/NO3– antiport transport activity (EC50,270s = 0.0017 mol %), and very low protonophoric activity. Electrostatic surface potential (ESP) and molecular lipophilicity potential (MLP) analyses show that a highly positive ESP at the CH-binding site and a uniformly lipophilic external surface are crucial for effectiveness. Overall, esterification of oligophenolic macrocycles provides a general route to CH-bonding anion receptors and transporters that approach the performance of the best NH-based systems and exhibit very low protonophoric activity, thus overcoming a key limitation of conventional hydrogen-bonding anionophores.
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BibTeX
@article{abdurakhmanova2026supramolecular,
title = {{Supramolecular Umpolung via Esterification: Converting Electron-Rich Phenolic Macrocycles into CH-Bonding Anion Receptors and Transporters}},
author = {Esma R. Abdurakhmanova and Bartłomiej Zawada and Marek P. Szymański and Piotr Cmoch and Renny M. Losus and Liliana Dobrzańska and Michał J. Chmielewski and Agnieszka Szumna},
journal = {JACS Au},
year = {2026},
month = oct,
doi = {10.1021/jacsau.6c01113},
url = {https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c01113/5454284/Supramolecular-Umpolung-via-Esterification},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Supramolecular Umpolung via Esterification: Converting Electron-Rich Phenolic Macrocycles into CH-Bonding Anion Receptors and Transporters
AU - Esma R. Abdurakhmanova
AU - Bartłomiej Zawada
AU - Marek P. Szymański
AU - Piotr Cmoch
AU - Renny M. Losus
AU - Liliana Dobrzańska
AU - Michał J. Chmielewski
AU - Agnieszka Szumna
PY - 2026
DA - 2026/10/20
JO - JACS Au
DO - 10.1021/jacsau.6c01113
UR - https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c01113/5454284/Supramolecular-Umpolung-via-Esterification
AB - CH-bonding anion receptors are supramolecular hosts that combine high chemical robustness, reduced propensity for deprotonation, and distinctive selectivity patterns, which make them attractive for transmembrane transport and medicinal applications. Their broader use is, however, limited by the scarcity of scaffolds capable of forming strong CH···anion interactions. Here, we present a general and operationally simple “supramolecular umpolung” strategy that converts π-electron-rich oligophenolic macrocycles into CH-bonding anion receptors and transporters via esterification of their OH groups. Resorcinarenes and pyrogallolarenes were transformed into acetyl (−OAc), triflate (−OTf), and pentafluorobenzenesulfonate (−OPFB) esters. The −OTf and −OPFB derivatives show high anion binding affinities across diverse media, while −OTf derivatives also act as excellent anion transporters in lipid bilayers, outperforming benchmark tetranitroresorcinarene. Per-triflated pyrogallolarene combines high chloride affinity (Ka ≈ 1010 M–1 in THF), outstanding Cl–/NO3– antiport transport activity (EC50,270s = 0.0017 mol %), and very low protonophoric activity. Electrostatic surface potential (ESP) and molecular lipophilicity potential (MLP) analyses show that a highly positive ESP at the CH-binding site and a uniformly lipophilic external surface are crucial for effectiveness. Overall, esterification of oligophenolic macrocycles provides a general route to CH-bonding anion receptors and transporters that approach the performance of the best NH-based systems and exhibit very low protonophoric activity, thus overcoming a key limitation of conventional hydrogen-bonding anionophores.
SN - 2691-3704
ER -