Würthner Frank
Center for Nanosystems Chemistry (CNC), Universität Würzburg, Theodor-Boveri-Weg, 97074 Würzburg, Germany.
Institut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
J Org Chem. 2022 Feb 4;87(3):1602-1615. doi: 10.1021/acs.joc.1c00625. Epub 2021 May 11.
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 (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.
对于超分子化学中的所有研究而言，合适溶剂的选择至关重要，这些研究包括主客体体系中的分子识别、分子内折叠、自组装以及超分子聚合。在本综述中，强调了线性自由能关系（LFERs）在揭示溶剂对配位键（如阳离子 - 冠醚）、氢键、卤键、偶极聚集和π - π堆积作用方面的有用性。对于超分子体系中广泛应用的所有这些分子间相互作用，吉布斯结合能与常见溶剂极性标度之间的LFER关系均可得到证明，这些标度包括基于溶剂化显色染料的(30)、π*、α或β，源自诸如古特曼给体和受体数或氢键给体和受体标度等结合过程的标度，或诸如柯克伍德 - 昂萨格或利普泰 - 昂萨格函数等物理函数。这些关系现在可用于更好地理解超分子相互作用中占主导地位的分子间作用力。它们还能使人们合理选择最适合制备自组装材料的溶剂，并估算结合常数，而无需对溶剂进行耗时的全面研究。
