Rühe Jessica, Rajeevan Megha, Shoyama Kazutaka, Swathi Rotti Srinivasamurthy, Würthner Frank
Institut für Organische Chemie, Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram (IISER TVM), Vithura, Thiruvananthapuram, 695551, India.
Angew Chem Int Ed Engl. 2024 Apr 22;63(17):e202318451. doi: 10.1002/anie.202318451. Epub 2024 Mar 18.
π-π interactions are among the most important intermolecular interactions in supramolecular systems. Here we determine experimentally a universal parameter for their strength that is simply based on the size of the interacting contact surfaces. Toward this goal we designed a new cyclophane based on terrylene bisimide (TBI) π-walls connected by para-xylylene spacer units. With its extended π-surface this cyclophane proved to be an excellent and universal host for the complexation of π-conjugated guests, including small and large polycyclic aromatic hydrocarbons (PAHs) as well as dye molecules. The observed binding constants range up to 10 M and show a linear dependence on the 2D area size of the guest molecules. This correlation can be used for the prediction of binding constants and for the design of new host-guest systems based on the herewith derived universal Gibbs interaction energy parameter of 0.31 kJ/molÅ in chloroform.
π-π相互作用是超分子体系中最重要的分子间相互作用之一。在此，我们通过实验确定了一个基于相互作用接触面大小的、用于描述其强度的通用参数。为实现这一目标，我们设计了一种基于对亚二甲苯基间隔单元连接的苝二酰亚胺（TBI）π壁的新型环芳。这种环芳因其扩展的π表面，被证明是一种优良且通用的主体，可用于络合π共轭客体，包括大小不同的多环芳烃（PAHs）以及染料分子。观察到的结合常数高达10 M，并且与客体分子的二维面积大小呈线性关系。这种相关性可用于预测结合常数，以及基于在氯仿中由此推导出的0.31 kJ/molÅ的通用吉布斯相互作用能参数来设计新的主客体体系。
