A general synthesis of cyclic bottlebrush polymers with enhanced mechanical properties via 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 (i.e., "grafting-through" polymerizations of macromonomers with ROMP) produce only ultrahigh molar mass cyclic bottlebrush polymers with poor molar mass control. Herein, we report a ring-expansion metathesis polymerization (REMP) approach to cyclic bottlebrush polymers via a "grafting-through" approach utilizing the active pyr-CB6 initiator developed in our lab. The resulting polymers, characterized via GPC-MALS-IV, are shown to have superior molar mass control across a range of target backbone lengths. The cyclic materials are also found to have superior mechanical properties when compared to their linear counterparts, as assessed by ball-mill grinding and compression testing experiments.

Efficient synthesis for each of the eight stereoisomers of the iminosugars lentiginosine and 1,4-dideoxy-1,4-imino-D-arabinitol (DAB).

Herein, we describe the efficient, diastereoselective syntheses of the iminosugars 1,4-dideoxy-1,4-imino-D-arabinitol (DAB) 1b, lentiginosine 3a, and the seven stereoisomers of each of these iminosugars starting from 4-benzoyl-6-deoxy-6-iodoglycopyranosides 47 with yields ranging from 38 % to 68 % for the DAB and isomers 1a-1h and from 44 % to 89 % for the lentiginosine and isomers 3a-3h. We also report the syntheses of the eight stereoisomers of the 4-benzoyl-6-deoxy-6-iodoglycopyranosides 47 from commercially available sugars. Key to the iminosugar syntheses is a single multistep reaction that converts the 4-benzoyl-6-deoxy-6-iodoglycopyranosides 47 to a vinyl pyrrolidine through a one-pot zinc mediated reductive elimination, followed by a reductive amination and finally an intramolecular nucleophilic substitution. Strategic selection of the amine utilized in the reductive amination and the functionalization of the intermediate carbon-carbon double bond provides access to a vast array of iminosugars.

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. We use dynamic mechanical analysis to demonstrate that the activation barrier to the glass transition process is significantly elevated for bullvalene-containing materials relative to "static" control networks. Furthermore, bullvalene rearrangements can be mechanically perturbed at low temperatures in the glassy region; such behavior facilitates energy dissipation (i.e., increased hysteresis energy) and polymer chain alignment to stiffen the material (i.e., increased Young's modulus) under load. Computational simulations corroborate our work that showcases bullvalene as a reversible "low-force" covalent mechanophore in the modulation of viscoelastic behavior.

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). By varying the amount of bullvalene incorporation within a poly(p-phenylene) chain (0-50 %), we can tune thermal properties and solution-state conformation. These features are caused by stochastic bullvalene isomers within the polymer backbone that result in kinked architectures. Synthetically, bullvalene incorporation offers a facile method to decrease structural rigidity within π-rich materials without concomitant crystallization. VT NMR experiments confirm that these materials remain dynamic in solution, offering the opportunity for future stimuli-responsive applications.