Lee Hyun, Lee Dongwhan
Department of Chemistry, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul, 08826, Korea.
Chemistry. 2023 Dec 1;29(67):e202302523. doi: 10.1002/chem.202302523. Epub 2023 Oct 24.
Nature utilizes an intimate stacking of aromatic motifs to construct functional structures, as demonstrated in protein folding and polynucleotide assembly. However, organized π-stacks of artificial molecules are difficult to build, primarily due to the weak, non-directional, and context-sensitive nature of van der Waals forces. To overcome these challenges, chemists have invented ingenious architectural designs to construct π-stacked supramolecular assemblies using clip-like molecules. This Concept article focuses on molecular clips that enable precise spatial control over assembly patterns, beyond the scope of simple host-guest chemistry. Different design strategies are analyzed and compared that leverage non-covalent interactions to create multi-layer π-stacks. Particular emphasis is placed on the choice of spine units as they play a crucial role in controlling the (i) spacing, (ii) orientation, and (iii) conformational pre-organization of linked aromatics to achieve long-range spatial ordering.
自然界利用芳香基序的紧密堆积来构建功能结构，这在蛋白质折叠和多核苷酸组装中得到了证明。然而，人工分子的有序π堆积很难构建，主要是由于范德华力具有弱、非定向和上下文敏感的性质。为了克服这些挑战，化学家们发明了巧妙的结构设计，以使用类夹子分子构建π堆积超分子组装体。这篇概念文章聚焦于分子夹子，它能够实现对组装模式的精确空间控制，超出了简单主客体化学的范畴。分析并比较了利用非共价相互作用创建多层π堆积的不同设计策略。特别强调了脊柱单元的选择，因为它们在控制连接芳烃的（i）间距、（ii）取向和（iii）构象预组织以实现长程空间有序方面起着至关重要的作用。
