%0 Journal Article %1 W_rthner_2021 %A Würthner, Frank %D 2021 %I American Chemical Society (ACS) %J J. Org. Chem %K myown %N 3 %P 1602--1615 %R 10.1021/acs.joc.1c00625 %T Solvent Effects in Supramolecular Chemistry: Linear Free Energy Relationships for Common Intermolecular Interactions %U https://doi.org/10.1021%2Facs.joc.1c00625 %V 87 %X The proper choice of solvent is of major importance for all studies in supramolecular chemistry, including molecular recognition in host−guest systems, intramolecular folding, self-assembly, and supramolecular polymerization. In this Perspective, the usefulness of linear free energy relationships (LFERs) is highlighted to unravel the effect of solvents on coordinate bonding (e.g., cation- crown ether), hydrogen bonding, halogen bonding, dipolar aggregation, and π−π- stacking. For all of these intermolecular interactions widely applied in supramolecular systems, LFER relationships between the Gibbs binding energies and common solvent polarity scales including ET(30), π*, α or β based on solvatochromic dyes, scales derived from binding processes such as Gutmann donor and acceptor numbers or hydrogen bond donor and acceptor scales, or physical functions like the Kirkwood−Onsager or the Liptay−Onsager functions could be demonstrated. These relationships can now be applied toward a better understanding of the prevailing intermolecular forces for supramolecular interactions. They further enable a rational selection of the most suitable solvent for the preparation of self-assembled materials and the estimation of binding constants without the need for time-consuming comprehensive investigations of solvents.

@article{W_rthner_2021, abstract = {The proper choice of solvent is of major importance for all studies in supramolecular chemistry, including molecular recognition in host−guest systems, intramolecular folding, self-assembly, and supramolecular polymerization. In this Perspective, the usefulness of linear free energy relationships (LFERs) is highlighted to unravel the effect of solvents on coordinate bonding (e.g., cation- crown ether), hydrogen bonding, halogen bonding, dipolar aggregation, and π−π- stacking. For all of these intermolecular interactions widely applied in supramolecular systems, LFER relationships between the Gibbs binding energies and common solvent polarity scales including ET(30), π*, α or β based on solvatochromic dyes, scales derived from binding processes such as Gutmann donor and acceptor numbers or hydrogen bond donor and acceptor scales, or physical functions like the Kirkwood−Onsager or the Liptay−Onsager functions could be demonstrated. These relationships can now be applied toward a better understanding of the prevailing intermolecular forces for supramolecular interactions. They further enable a rational selection of the most suitable solvent for the preparation of self-assembled materials and the estimation of binding constants without the need for time-consuming comprehensive investigations of solvents.}, added-at = {2022-02-07T12:47:17.000+0100}, author = {Würthner, Frank}, biburl = {https://www.bibsonomy.org/bibtex/2c7389cffbaafb05fc780e49388dd100d/wuerthner_group}, doi = {10.1021/acs.joc.1c00625}, interhash = {0c66d9779070c7e1ba86e3952dce97b6}, intrahash = {c7389cffbaafb05fc780e49388dd100d}, journal = {J. Org. Chem}, keywords = {myown}, month = may, number = 3, pages = {1602--1615}, publisher = {American Chemical Society ({ACS})}, timestamp = {2022-02-07T12:47:17.000+0100}, title = {Solvent Effects in Supramolecular Chemistry: Linear Free Energy Relationships for Common Intermolecular Interactions}, url = {https://doi.org/10.1021%2Facs.joc.1c00625}, volume = 87, year = 2021 }