The reaction of tetranitropolyamino carriers with 4-tert-butylphenyl isocyanate gives rise to ureido-based receptors. These receptors vary in the acidity of their bridging NH groups on supporting skeletons, significantly affecting their complexation ability. While introducing nonbasic anions leads to the independent action of ureido-binding sites, accomplished with low binding efficiency for all studied compounds, the results for basic anions depend on the system used. Here, due to a different electron density distribution on supporting skeletons, the interaction with basic anions may cause unwanted deprotonation (acyclic systems 5) or lead to anion complexation (macrocycles 6 and 7). Moreover, in the case of tetraureido azacalix[4]arene 6, the addition of carboxylates and phosphate induces system cooperativity, which changes the complex stoichiometry from 1:4 to a 1:2 ratio (receptor: anion) and positively improves binding efficiency.

Aix Marseille Université CNRS UMR 7325 Centre Interdisciplinaire de Nanoscience de Marseille Campus de Luminy Marseille cedex 09 13288 France

Department of Analytical Chemistry University of Chemistry and Technology Prague Technicka 5 Prague 6 166 28 Czech Republic

Department of Organic Chemistry University of Chemistry and Technology Prague Technicka 5 Prague 6 166 28 Czech Republic

Department of Physical Chemistry University of Chemistry and Technology Prague Technicka 5 Prague 6 166 28 Czech Republic

Institute of Chemical Process Fundamentals of Czech Academy of Sciences v v i Rozvojová 135 Prague 6 16502 Czech Republic

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Sessler, J. L. ; Gale, P. ; Cho, W.-S. . Anion Receptor Chemistry; The Royal Society of Chemistry, 2006.

Molina P., Zapata F., Caballero A.. Anion Recognition Strategies Based on Combined Noncovalent Interactions. Chem. Rev. 2017;117(15):9907–9972. doi: 10.1021/acs.chemrev.6b00814. PubMed DOI

Springer Anion Recognition in Supramolecular Chemistry; Springer: Berlin, Heidelberg, 2011. 10.1007/978-3-642-15444-7. DOI

Busschaert N., Caltagirone C., Van Rossom W., Gale P. A.. Applications of Supramolecular Anion Recognition. Chem. Rev. 2015;115(15):8038–8155. doi: 10.1021/acs.chemrev.5b00099. PubMed DOI

McNaughton D. A., Ryder W. G., Gilchrist A. M., Wang P., Fares M., Wu X., Gale P. A.. New Insights and Discoveries in Anion Receptor Chemistry. Chem. 2023;9(11):3045–3112. doi: 10.1016/j.chempr.2023.07.006. DOI

Patrick S. C., Beer P. D., Davis J. J.. Solvent Effects in Anion Recognition. Nat. Rev. Chem. 2024;8(4):256–276. doi: 10.1038/s41570-024-00584-4. PubMed DOI

Macreadie L. K., Gilchrist A. M., McNaughton D. A., Ryder W. G., Fares M., Gale P. A.. Progress in Anion Receptor Chemistry. Chem. 2022;8(1):46–118. doi: 10.1016/j.chempr.2021.10.029. DOI

Gale A. P., Howe E. N. W., Wu X.. Anion Receptor Chemistry. Chem. 2016;1(3):351–422. doi: 10.1016/j.chempr.2016.08.004. DOI

Taylor M. S.. Anion Recognition Based on Halogen, Chalcogen, Pnictogen and Tetrel Bonding. Coord. Chem. Rev. 2020;413:213270. doi: 10.1016/j.ccr.2020.213270. DOI

He X., Thompson R. R., Clawson S. A., Fronczek F. R., Lee S.. Anion Receptors with Nitrone C–H Hydrogen Bond Donors. Chem. Commun. 2023;59(31):4624–4627. doi: 10.1039/D3CC00371J. PubMed DOI

Barišić D., Lešić F., Tireli Vlašić M., Užarević K., Bregović N., Tomišić V.. Anion Binding by Receptors Containing NH Donating Groups – What Do Anions Prefer? Tetrahedron. 2022;120:132875. doi: 10.1016/j.tet.2022.132875. DOI

Caltagirone C., Bates G. W., Gale P. A., Light M. E.. Anion Binding vs.Sulfonamide Deprotonation in Functionalised Ureas. Chem. Commun. 2008;1:61–63. doi: 10.1039/B713431B. PubMed DOI

Salvadori K., Šimková L., Císařová I., Sýkora J., Ludvík J., Cuřínová P.. Sulphonamidic Groups as Electron-Withdrawing Units in Ureido-Based Anion Receptors: Enhanced Anion Complexation versus Deprotonation. ChemPlusChem. 2020;85(7):1401–1411. doi: 10.1002/cplu.202000326. PubMed DOI

Gómez D. E., Fabbrizzi L., Licchelli M., Monzani E. U. V.. Thiourea in Anion Recognition. Org. Biomol. Chem. 2005;3(8):1495–1500. doi: 10.1039/B500123D. PubMed DOI

Etter M. C., Urbanczyk-Lipkowska Z., Zia-Ebrahimi M., Panunto T. W.. Hydrogen Bond-directed Cocrystallization and Molecular Recognition Properties of Diarylureas. J. Am. Chem. Soc. 1990;112(23):8415–8426. doi: 10.1021/ja00179a028. DOI

Boiocchi M., Del Boca L., Gómez D. E., Fabbrizzi L., Licchelli M., Monzani E.. Nature of Urea–Fluoride Interaction: Incipient and Definitive Proton Transfer. J. Am. Chem. Soc. 2004;126(50):16507–16514. doi: 10.1021/ja045936c. PubMed DOI

Bregović V. B., Basarić N., Mlinarić-Majerski K.. Anion Binding with Urea and Thiourea Derivatives. Coord. Chem. Rev. 2015;295:80–124. doi: 10.1016/j.ccr.2015.03.011. DOI

Amendola V., Fabbrizzi L., Mosca L.. Anion Recognition by Hydrogen Bonding: Urea-based Receptors. Chem. Soc. Rev. 2010;39(10):3889–3915. doi: 10.1039/b822552b. PubMed DOI

Klejch T., Slavíček J., Hudeček O., Eigner V., Gutierrez N. A., Cuřínová P., Lhoták P.. Calix­[4]­arenes Containing a Ureido Functionality on the Lower Rim as Highly Efficient Receptors for Anion Recognition. New J. Chem. 2016;40(9):7935–7942. doi: 10.1039/C6NJ01271J. DOI

Surina A., Čejka J., Salvadori K., Lhoták P.. Anion Recognition Using meta-substituted Ureidocalix[4]­arene Receptors. Org. Biomol. Chem. 2024;22(43):8669–8678. doi: 10.1039/D4OB01441C. PubMed DOI

Cvetnić M., Cindro N., Topić E., Bregović N., Tomišić V.. Supramolecular Handshakes: Characterization of Urea-Carboxylate Interactions Within Calixarene Frameworks. ChemPlusChem. 2024;89(7):e202400130. doi: 10.1002/cplu.202400130. PubMed DOI

Augusto A. S., Miranda A. S., Ascenso J. R., Miranda M. Q., Félix V., Brancatelli G., Hickey N., Geremia S., Marcos P. M.. Anion Recognition by Partial Cone Dihomooxacalix[4]­arene-Based Receptors Bearing Urea Groups: Remarkable Affinity for Benzoate Ion. Eur. J. Org. Chem. 2018;2018(41):5657–5667. doi: 10.1002/ejoc.201800880. DOI

Shimizu K. D., Rebek J.. Synthesis and Assembly of Self-complementary Calix[4]­arenes. Proc. Natl. Acad. Sci. U. S. A. 1995;92(26):12403–12407. doi: 10.1073/pnas.92.26.12403. PubMed DOI PMC

Cvetnić M., Cindro N., Bregović N., Tomišić V.. Thermodynamics of Anion Binding by (Thio)­ureido-calix[4]­arene Derivatives in Acetonitrile. ACS Phys. Chem. Au. 2024;4(6):773–786. doi: 10.1021/acsphyschemau.4c00077. PubMed DOI PMC

Budka J., Lhotak P., Michlova V., Stibor I.. Urea Derivatives of Calix[4]­arene 1,3-alternate: an Anion Receptor with Profound Negative Allosteric Effect. Tetrahedron Lett. 2001;42(8):1583–1586. doi: 10.1016/S0040-4039(00)02309-1. DOI

Touil M., Lachkar M., Siri O.. Metal-free Synthesis of Azacalix[4]­arenes. Tetrahedron Lett. 2008;49(51):7250–7252. doi: 10.1016/j.tetlet.2008.10.008. DOI

Konishi H., Hashimoto S., Sakakibara T., Matsubara S., Yasukawa Y., Morikawa O., Kobayashi K.. Synthesis and Conformational Properties of Tetranitroazacalix[4]­arenes. Tetrahedron Lett. 2009;50(6):620–623. doi: 10.1016/j.tetlet.2008.11.095. DOI

Touil M., Elhabiri M., Lachkar M., Siri O.. Synthesis and Properties of the Emerging Azacalix­[14]­arenes. Eur. J. Org. Chem. 2011;2011(10):1914–1921. doi: 10.1002/ejoc.201001432. DOI

Pascal S., Lavaud L., Azarias C., Varlot A., Canard G., Giorgi M., Jacquemin D., Siri O.. Azacalixquinarenes: From Canonical to (Poly-)­Zwitterionic Macrocycles. J. Org. Chem. 2019;84(3):1387–1397. doi: 10.1021/acs.joc.8b02847. PubMed DOI

Chen Z., Giorgi M., Jacquemin D., Elhabiri M., Siri O.. Azacalixphyrin: The Hidden Porphyrin Cousin Brought to Light. Angew. Chem., Int. Ed. 2013;52(24):6250–6254. doi: 10.1002/anie.201301217. PubMed DOI

Wang D.-X., Wang M.-X.. Anion Recognition by Charge Neutral Electron-deficient Arene Receptors. Chimia. 2011;65(12):939. doi: 10.2533/chimia.2011.939. PubMed DOI

Canard G., Edzang J. A., Chen Z., Chessé M., Elhabiri M., Giorgi M., Siri O.. 1,3-Alternate Tetraamido-Azacalix[4]­arenes as Selective Anion Receptors. Chem. - Eur. J. 2016;22(16):5756–5766. doi: 10.1002/chem.201505089. PubMed DOI

Thordarson, P. Online tools for supramolecular chemistry research and analysis 2025. http://supramolecular.org Accessed 18 October 2025.

Webb J. E. A., Crossley M. J., Turner P., Thordarson P.. Pyromellitamide Aggregates and Their Response to Anion Stimuli. J. Am. Chem. Soc. 2007;129(22):7155–7162. doi: 10.1021/ja0713781. PubMed DOI

Schalley, C. A. Analytical methods in supramolecular chemistry; John Wiley & Sons, 2012.

Salvadori K., Krupková A., Š’astná L. Č., Müllerová M., Eigner V., Strašák T., Cuřínová P.. Controlled Anchoring of (Phenylureido)­sulfonamide-Based Receptor Moieties: An Impact of Binding Site Multiplication on Complexation Properties. Molecules. 2021;26(18):5670. doi: 10.3390/molecules26185670. PubMed DOI PMC

Chutia R., Dey S. K., Das G.. Self-Assembly of a Tris­(Urea) Receptor as Tetrahedral Cage for the Encapsulation of a Discrete Tetrameric Mixed Phosphate Cluster (H2PO4 –•HPO4 2–)2 . Cryst. Growth Des. 2015;15(10):4993–5001. doi: 10.1021/acs.cgd.5b00926. DOI

Wang C., Du M., Ruan F., He Y., Cai Y., Kong L., Hu X.. Exploiting the Dimerization Characteristic of H2PO4 – to Promote Its Selective Recognition by a Tetra-Amido Macrocycle. J. Org. Chem. 2025;90(19):6468–6477. doi: 10.1021/acs.joc.5c00279. PubMed DOI

Guo S.-Y., Guo Q.-H., Tong S., Wang M.-X.. Synthesis of Electron-Deficient Corona[5]­arenes and Their Selective Complexation with Dihydrogen Phosphate: Cooperative Effects of Anion−π Interactions. Angew. Chem., Int. Ed. 2020;59(21):8078–8083. doi: 10.1002/anie.201915839. PubMed DOI