A Dendronized Polymer Is a Single-Molecule Glass

The molecular architecture of dendronized polymers can be tuned to obtain nanoscale objects with desired properties. In this paper, we bring together experiments and computer simulations to study the thermodynamic and dynamic properties of a single dendronized polymer chain. We find that, upon changing certain architectural features, dynamic correlations characterizing backbone conformational fluctuations of a dendronized polymer exhibit dynamics akin to glass-forming bulk liquids. Thus, a dendronized polymer chain is a novel macromolecule that is a single-molecule glass. Over a range of conditions that lead to glassy dynamics, there does not appear to be any thermodynamic singularities. We discuss how a dendronized polymer is a molecular system that can directly test different models of glassy dynamics. We also show that defect densities characteristic of typical synthesis conditions do not alter the material properties of dendronized polymers.