A general synthesis of cyclic bottlebrush polymers with enhanced mechanical properties graft-through ring expansion metathesis polymerization.

Bottlebrush polymers represent an important class of macromolecular architectures, with applications ranging from drug delivery to organic electronics. While there is an abundance of literature describing the synthesis, structure, and applications of linear bottlebrush polymers using ring-opening metathesis polymerization (ROMP), there are comparatively less reports on their cyclic counterparts. This lack of research is primarily due to the difficulty in synthesizing cyclic bottlebrush polymers, as extensions of typical routes towards linear bottlebrush polymers (, "grafting-through" polymerizations of macromonomers with ROMP) produce only ultrahigh molar mass cyclic bottlebrush polymers with poor molar mass control.

Molecular Ball Joints: Mechanochemical Perturbation of Bullvalene Hardy-Cope Rearrangements in Polymer Networks.

The solution-state fluxional behavior of bullvalene has fascinated physical organic and supramolecular chemists alike. Little effort, however, has been put into investigating bullvalene applications in bulk, partially due to difficulties in characterizing such dynamic systems. To address this knowledge gap, we herein probe whether bullvalene Hardy-Cope rearrangements can be mechanically perturbed in bulk polymer networks.

Stochastic Bullvalene Architecture Modulates Structural Rigidity in π-Rich Macromolecules.

The synthesis and processing of π-rich polymers found in novel electronics and textiles is difficult because chain stiffness leads to low solubility and high thermal transitions. The incorporation of "shape-shifting" molecular cages into π-rich backbone provides an ensemble of structural kinks to modulate chain architecture via a self-contained library of valence isomers. In this work, we report the synthesis and characterization of (bullvalene-co-phenylene)s that feature smaller persistence lengths than a prototypical rigid rod polymer, poly(p-phenylene).