Publication details
Two Squares in a Barrel: An Axially Disubstituted Conformationally Rigid Aliphatic Binding Motif for Cucurbit[6]uril
| Authors | |
|---|---|
| Year of publication | 2023 |
| Type | Article in Periodical |
| Magazine / Source | Journal of Organic Chemistry |
| MU Faculty or unit | |
| Citation | |
| 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. |