Oshchepkov Alexander S, Korenkov Konstantin, Sarkar Sayan, Papaianina Olena, Akhmetov Vladimir A, Ruppenstein Cordula, Troyanov Sergey I, Sharapa Dmitry I, Amsharov Konstantin Y, Kataev Evgeny A
Department of Physics, Max Planck Institute for the Science of Light, D-91058 Erlangen, Germany.
Institute of Chemistry, Organic Chemistry, Martin-Luther-University Halle-Wittenberg, 06120 Halle, Germany.
JACS Au. 2025 Mar 13;5(4):1803-1811. doi: 10.1021/jacsau.5c00049. eCollection 2025 Apr 28.
The curvature of an aromatic system is an essential parameter that can be used to program the self-assembly and host-guest complementarity in geodesic polyarenes. However, the challenging synthesis of curved aromatics impedes exploration of the related effects on the binding properties. The design and synthesis of a polyarene with programmed curvature fitting to C by a stepwise introduction of five-membered rings are presented to solve this challenge. Among several methods explored, the route utilizing cyclodehydrofluorination proved to be the most successful, in terms of the highest product yield. The binding studies suggest that fine-tuning the curvature in acyclic systems leads to a dramatic increase in affinity, embedding specific binding modes and selectivity, as revealed from the comparative studies with C and C. Experimental and theoretical investigations with curved polyarenes of different sizes show that the buried surface area upon binding has a linear correlation with the binding energies. The curvature complementarity appeared to play a decisive role in achieving selective recognition of C via the formation of a 2:1 complex along the major axis with an overall constant of 10 M and positive cooperativity. The developed nanoribbons bearing the curvature of C is the first allcarbon host showing binding affinities for fullerenes that are comparable with macrocyclic [10]CPP. The obtained data pave the way for understanding the properties of geodesic polyarenes and the design of new self-assembled materials based on fullerenes, nanotubes, and other curved structures.
芳香体系的曲率是一个重要参数，可用于调控测地线型多芳烃的自组装和主客体互补性。然而，弯曲芳烃具有挑战性的合成过程阻碍了对其结合性质相关影响的探索。本文提出通过逐步引入五元环来设计和合成一种曲率符合C的多芳烃，以解决这一挑战。在探索的几种方法中，就最高产物产率而言，利用环脱氟氢化反应的路线被证明是最成功的。结合研究表明，在非环状体系中微调曲率会导致亲和力显著增加，嵌入特定的结合模式和选择性，这从与C和C的对比研究中可以看出。对不同尺寸弯曲多芳烃的实验和理论研究表明，结合时的埋藏表面积与结合能呈线性相关。曲率互补性似乎在通过沿主轴形成2:1配合物（总常数为10 M且具有正协同性）实现对C的选择性识别中起决定性作用。所开发的具有C曲率的纳米带是首个对富勒烯具有与大环[10]CPP相当的结合亲和力的全碳主体。所获得的数据为理解测地线型多芳烃的性质以及基于富勒烯、纳米管和其他弯曲结构的新型自组装材料的设计铺平了道路。
