Journal article

Publication year: 2022

Journal: Chemistry - A European Journal

Volume number: 28

Issue number: 38

ISSN: 0947-6539

eISSN: 1521-3765

Open access status: Green

DOI Link: https://doi.org/10.1002/chem.202200529

Publisher: Wiley

Abstract: 
The rationalization of non-covalent binding trends is both of fundamental interest and provides new design concepts for biomimetic molecular systems. Cucurbit[n]urils (CBn) are known for a long time as the strongest synthetic binders for a wide range of (bio)organic compounds in water. However, their host-guest binding mechanism remains ambiguous despite their symmetric and simple macrocyclic structure and the wealth of literature reports. We herein report experimental thermodynamic binding parameters (Delta G, Delta H, T Delta S) for CB7 and CB8 with a set of hydroxylated adamantanes, di-, and triamantanes as uncharged, rigid, and spherical/ellipsoidal guests. Binding geometries and binding energy decomposition were obtained from high-level theory computations. This study reveals that neither London dispersion interactions, nor electronic energies or entropic factors are decisive, selectivity-controlling factors for CBn complexes. In contrast, peculiar host-related solvation effects were identified as the major factor for rationalizing the unique behavior and record-affinity characteristics of cucurbit[n]urils.

Harvard Citation style: Grimm, L., Spicher, S., Tkachenko, B., Schreiner, P., Grimme, S. and Biedermann, F. (2022) The Role of Packing, Dispersion, Electrostatics, and Solvation in High-Affinity Complexes of Cucurbit[n]urils with Uncharged Polar Guests, Chemistry - A European Journal, 28(38), Article e202200529. https://doi.org/10.1002/chem.202200529

APA Citation style: Grimm, L., Spicher, S., Tkachenko, B., Schreiner, P., Grimme, S., & Biedermann, F. (2022). The Role of Packing, Dispersion, Electrostatics, and Solvation in High-Affinity Complexes of Cucurbit[n]urils with Uncharged Polar Guests. Chemistry - A European Journal. 28(38), Article e202200529. https://doi.org/10.1002/chem.202200529