Efficient modification with flexible spacing coating for in situ reversible assembly of semirigid macroscopic objects through hierarchical metal coordination

Abstract

Macroscopic supramolecular assembly plays a key role to bridge the fundamental researches on molecular recognition to the potential applications as supramolecular materials. However, the challenge remains to promote the research from soft hydrogel system to semirigid objects or building blocks. Herein, the concept of flexible spacing coating was employed to modify the model polydimethylsiloxane building blocks, and reversible macroscopic assembly was successfully realized through introducing highly directional, dynamic, and reversible coordinate interactions as driving forces. The driving force for the macroscopic assembly was confirmed by introducing highly competitive ethylene diamine tetra acetic acid solution as an orthodox system to disassemble the assembled blocks. Moreover, the coordinate interaction was further understood through unique in situ measurements of binding forces between building blocks during assembly process. This work of macroscopic supramolecular assembly provides an in situ visible platform, which is significant to clarify the highly fascinating and facile coordinate interactions on the macroscopic assembly behavior. To increase understanding of macroscopic assembly with flexible spacing coating, a fascinating noncovalent interaction that can be employed in macroscopic assembly is coordinate interactions. Selfassembly through coordinate interactions has emerged as a wellestablished methodology, and metal-ligand interactions have been employed in construction of metallosupramolecular structures very frequently. A variety of elaborate metallosupramolecules, from 2-dimensional polygons to 3-dimensional cages, prisms, and polyhedra,

The macroscopic shape of assemblies formed from microparticles based on host–guest interaction dependent on the guest content

“…In these decades, biological macroscopic assemblies have inspired researchers to utilize molecular recognition to develop smart materials 1 – 3 , e.g., soft actuators 4 – 9 and self-healing materials 10 – 25 . Recently, macroscopic self-assemblies, which allow ones to see molecular recognition by naked eyes, have been realized using millimeter-scale hydrogel pieces possessing molecular recognition moieties 26 – 30 . Even if the difference in binding constants of molecular recognition moieties is small, the systems of mixture of gel pieces can exhibit perfect fidelity by controlling the contents of molecular recognition moieties 31 – 33 .…”

Viscoelastic properties and self‐healing behavior in a family of supramolecular ionic blends from silicone functional oligomers

“…Over the last years, important advances have been made in the field of smart materials, especially for intrinsic self-healing polymer materials, which exploit dynamic bonds, typically generated by supramolecular chemistry approaches, to create self-assembling networks. 1,2 Noncovalent cross-linked systems via supramolecular interactions, such as π-π stacking, [3][4][5] ionic interactions (eg, ionomers), [6][7][8] metal-ligand associations [9][10][11][12] and, in most cases, hydrogen-bonding interactions, [13][14][15][16][17][18][19] have been developed and characterized for this purpose. In some cases, the approach relies on the modification of polymers with functional groups that can interact with each other through explicit strong or weak associations, resulting in the formation of a phase different from the bulk polymer.…”

The macroscopic shape of assemblies formed from microparticles based on host–guest interaction dependent on the guest content

“…In these decades, biological macroscopic assemblies have inspired researchers to utilize molecular recognition to develop smart materials, e.g., soft actuators [1][2][3][4][5][6] and self-healing materials [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] . Recently, macroscopic selfassemblies, which allow ones to see molecular recognition by naked eyes, have been realized using millimeter-scale hydrogel pieces possessing molecular recognition moieties [23][24][25][26][27] . Even if the difference in binding constants of molecular recognition moieties is small, the systems of mixture of gel pieces can exhibit perfect delity by controlling the contents of molecular recognition moieties [28][29][30] .…”