Two Squares in a Barrel: An Axially Disubstituted Conformationally Rigid Aliphatic Binding Motif for Cucurbit[6]uril

• Authors: JELINKOVA Kristyna; ZAVODNA Aneta; KALETA Jiri; JANOVSKY Petr; ZATLOUKAL Filip; NEČAS Marek; PRUCKOVA Zdenka; DASTYCHOVA Lenka; ROUCHAL Michal; VICHA Robert
• Year of publication: 2023
• Type: Article in Periodical
• Magazine / Source: Journal of Organic Chemistry
• MU Faculty or unit: Faculty of Science
• Citation: JELINKOVA, Kristyna, Aneta ZAVODNA, Jiri KALETA, Petr JANOVSKY, Filip ZATLOUKAL, Marek NEČAS, Zdenka PRUCKOVA, Lenka DASTYCHOVA, Michal ROUCHAL and Robert VICHA. Two Squares in a Barrel: An Axially Disubstituted Conformationally Rigid Aliphatic Binding Motif for Cucurbit[6]uril. Journal of Organic Chemistry. WASHINGTON: AMER CHEMICAL SOC, 2023, vol. 88, No 22, p. 15615-15625. ISSN 0022-3263. Available from: https://dx.doi.org/10.1021/acs.joc.3c01556.
• web: https://pubs.acs.org/doi/10.1021/acs.joc.3c01556
• Doi: http://dx.doi.org/10.1021/acs.joc.3c01556
• Keywords: HOST-GUEST BINDING; AFFINITY; MOVEMENT; ROTAXANE; SENSOR; CAVITY; MODES; SALTS
• Description: Novel binding motifs suitable for the construction of multitopic guest-based molecular devices (e.g., switches, sensors, data storage, and catalysts) are needed in supramolecular chemistry. No rigid, aliphatic binding motif that allows for axial disubstitution has been described for cucurbit[6]uril (CB6) so far. We prepared three model guests combining spiro[3.3]heptane and bicyclo[1.1.1]pentane centerpieces with imidazolium and ammonium termini. We described their binding properties toward CB6/7 and alpha-/beta-CD using NMR, titration calorimetry, mass spectrometry, and single-crystal X-ray diffraction. We found that a bisimidazolio spiro[3.3]heptane guest forms inclusion complexes with CB6, CB7, and beta-CD with respective association constants of 4.0 x 10(4), 1.2 x 10(12), and 1.4 x 10(2). Due to less hindering terminal groups, the diammonio analogue forms more stable complexes with CB6 (K = 1.4 x 10(6)) and CB7 (K = 3.8 x 10(12)). The bisimidazolio bicyclo[1.1.1]pentane guest forms a highly stable complex only with CB7 with a K value of 1.1 x 10(11). The high selectivity of the new binding motifs implies promising potential in the construction of multitopic supramolecular components.