Institut für Organische Chemie and Center for Nanosystems Chemistry, Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, 350116, China.
Angew Chem Int Ed Engl. 2022 Apr 4;61(15):e202117625. doi: 10.1002/anie.202117625. Epub 2022 Feb 18.
Enantioselective molecular recognition of chiral molecules that lack specific interaction sites for hydrogen bonding or Lewis acid-base interactions remains challenging. Here we introduce the concept of tailored chiral π-surfaces toward the maximization of shape complementarity. As we demonstrate for helicenes it is indeed possible by pure van-der-Waals interactions (π-π interactions and CH-π interactions) to accomplish enantioselective binding. This is shown for a novel benzo[ghi]perylene trisimide (BPTI) receptor whose π-scaffold is contorted into a chiral plane by functionalization with 1,1'-bi-2-naphthol (BINOL). Complexation experiments of enantiopure (P)-BPTI with (P)- and (M)-[6]helicene afforded binding constants of 10 700 M and 550 M , respectively, thereby demonstrating the pronounced enantiodifferentiation by the homochiral π-scaffold of the BPTI host. The enantioselective recognition is even observable by the naked eye due to a specific exciplex-type emission originating from the interacting homochiral π-scaffolds of electron-rich [6]helicene and electron-poor BPTI.
手性分子缺乏氢键或路易斯酸碱相互作用的特定相互作用位点，其对映选择性分子识别仍然具有挑战性。在这里，我们引入了针对手性π-面的定制概念，以最大限度地提高形状互补性。正如我们为螺旋芴所证明的那样，通过纯范德华相互作用（π-π相互作用和 CH-π相互作用）确实可以实现对映选择性结合。这是通过用 1,1'-双-2-萘酚（BINOL）功能化扭曲成手性平面的新型苯并[ghi]苝三酰亚胺（BPTI）受体来实现的。对映纯（P）-BPTI 与（P）-和（M）-[6]螺旋芴的络合实验分别提供了 10700 M 和 550 M 的结合常数，从而证明了 BPTI 主体的同手性π-支架明显的对映体分化。由于来自富电子[6]螺旋芴和缺电子 BPTI 的相互作用同手性π-支架的特定激基型发射，甚至可以通过肉眼观察到对映选择性识别。
