Assembling Molecular Clips To Build π-Stacks

Abstract

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.