Abstract
Chiral molecular switches are attracting attention as they could pave the way to chiral molecular machines. Herein, we report on the design and synthesis of a single molecule chiral switch based on a cyclotriveratrylene scaffold, in which the chirality inversion is controlled by the solvent. Hemicryptophanes are built around a C3 cyclotriveratrylene chiral unit, with either M or P handedness, connected to another tripod and usually displaying an “out” configuration. Here, we demonstrate that solvents are able to control the “in” and “out” configurations of the CTV unit, creating a chiral molecular switch from (M/P)”in” to (P/M)”out” handedness. The full characterization of the “in” and “out” configurations and of the chirality switch were made possible by combining NMR, HPLC, ECD, DFT and molecular dynamics. Interestingly, bulky aromatic solvents such as 2-t-butylphenol favor the “in” configuration while polar aprotic solvents such as acetone favor the “out” configuration. This chiral switch was found to be fully reversible allowing the system to oscillate between two different M and P configurations several times upon the action of solvents stimuli.
| Original language | English |
|---|---|
| Article number | e202303294 |
| Journal | Chemistry - A European Journal |
| Volume | 30 |
| Issue number | 8 |
| DOIs | |
| Publication status | Published - 7 Feb 2024 |
| Externally published | Yes |
Funding
Y.C. and A.M. thank the Agence Nationale de la Recherche for funding the APICOCAT project, grant ANR-21-CE07-0011 and the Co-LAB project, grant ANR-19-CE07-0024. We would like to thank Michel Giorgi for the resolution of X-ray structures, Sabine Chevallier Michaud for low resolution mass spectrometry and the Spectropole in Marseille for characterizations. We thank the \u2018Centre de Calcul Intensif d\u2032Aix-Marseille\u2019 for granting us access to its high-performance computing resources. Y.C. and A.M. thank the Agence Nationale de la Recherche for funding the APICOCAT project, grant ANR\u201021\u2010CE07\u20100011 and the Co\u2010LAB project, grant ANR\u201019\u2010CE07\u20100024. We would like to thank Michel Giorgi for the resolution of X\u2010ray structures, Sabine Chevallier Michaud for low resolution mass spectrometry and the Spectropole in Marseille for characterizations. We thank the \u2018Centre de Calcul Intensif d\u2032Aix\u2010Marseille\u2019 for granting us access to its high\u2010performance computing resources.
| Funders | Funder number |
|---|---|
| Agence Nationale de la Recherche | ANR‐19‐CE07‐0024, ANR-21-CE07-0011 |
Keywords
- cage compounds
- chirality
- cyclotriveratrylene
- molecular switch
- solvent effects