Macroscopic Supramolecular Assembly through Electrostatic Interactions Based on a Flexible Spacing Coating

Macroscopic supramolecular assembly (MSA) is a recent advance in supramolecular chemistry that involves associating large building blocks with a size larger than 10 µm through noncovalent interactions. However, until now the applicable material system is rather limited to hydrogels, and MSA of rigid materials with supramolecular interactions widely used in molecular assembly has rarely been reported due to the difficulty in achieving multivalency between rigid surfaces. Herein, the concept of flexible spacing coating is applied with highly flowable properties, and the electrostatic‐interaction‐driven MSA of relatively rigid polydimethylsiloxane building blocks is demonstrated. With the flexible spacing coating of a polyelectrolyte multilayer, the oppositely charged rigid building blocks can realize MSA under shaking in water for 5 min. The major contribution of the electrostatic interaction is confirmed by both qualitative controlled MSA experiments in other solvents, disassembly in ionic solution and quantitative results with an in situ force measurement method. Macroscopic supramolecular assembly (MSA) is a recent advance in supramolecular chemistry but currently limited to applicable materials and supramolecular interactions. This works demonstrates the first electrostatic‐interaction‐driven MSA of rigid building blocks based on the concept of flexible spacing coating, thus having broadened the applicable building blocks and extended practical application conditions of MSA.