Topological Interaction among Molecular Cluster Assemblies Affords Tunable Viscoelasticity.

In the assemblies of subnanoscale polyhedral oligomeric silsesquioxane, topological interaction makes the dominant contribution to their viscoelasticity with broad tunability. The assembly molecules are designed with dumbbell, triangular, and tetrahedral shapes, and they demonstrate an intrinsic glassy feature with neither long-range ordering nor supramolecular assembly formation in their bulk. Their viscoelasticity can be broadly tuned through the tailoring of molecular topologies, while the trimer and tetramer assemblies afford elastic moduli comparable to those of rubbers (∼0.5 MPa) even 80 K above their glass transition temperatures. Molecular dynamics studies reveal the topological constraints resulting from the topology-disrupted cooperative dynamics among the cluster assemblies, and this finally leads to the typical caging dynamics of the structural units and the elasticity of the bulk materials. Further broadband dielectric spectroscopy studies uncover the unique hierarchical relaxation dynamics, inspiring the strategy for the decoupling of mechanical strengths and toughness for the design of impact resistant materials.