Photoresponsive Viscoelasticity of the Granular Materials of Azobenzene-Bearing Molecular Nanoparticles.

Abstract

The large sizes of granular particles lead to their slow diffusive dynamics and significant interparticle friction, bringing enormous difficulty to tune the mechanical properties and processability of the granular materials (GMs). Herein, 1 nm polyhedral oligomeric silsesquioxane (POSS) particles functionalized with azobenzene are designed as structural units, and the obtained GMs show unique photoswitchable viscoelasticity. The azobenzene group can undergo a reversible trans-cis conformation switch while the π-π stacking among the azobenzene fragments is only favored by the trans-conformation due to molecular geometrical requirements. The POSS units from neighboring assemblies close pack to form microdomains, and the POSS is under confinement by both the supramolecular bonding and the other POSS in the microdomains. The simultaneous breaking of the two types of confinement is difficult and, therefore, the free diffusion of POSS is hindered, leading to the elasticity of the GMs of trans-POSS. For cis-POSS, the interparticle supramolecular interaction is weak and the POSS unit can undergo free diffusion, contributing to their high flowability at room temperature. The photoswitching viscoelasticity of GMs is further used for self-healing and photoswitchable adhesion. This work paves new pathways for the regulation of material viscoelasticity and the design of GM-based smart materials.