Peiguan B. Sun, Meredith N. Pomfret, Matthew J. Elardo, Adhya Suresh, Ángel Rentería-Gómez, Remy F. Lalisse, Sheila Keating, Chuqiao Chen, Shayna L. Hilburg, Progyateg Chakma, Yunze Wu, Rowina C. Bell, Stuart J. Rowan, Osvaldo Gutierrez and Matthew R. Golder*,
{"title":"Molecular Ball Joints: Mechanochemical Perturbation of Bullvalene Hardy–Cope Rearrangements in Polymer Networks","authors":"Peiguan B. Sun, Meredith N. Pomfret, Matthew J. Elardo, Adhya Suresh, Ángel Rentería-Gómez, Remy F. Lalisse, Sheila Keating, Chuqiao Chen, Shayna L. Hilburg, Progyateg Chakma, Yunze Wu, Rowina C. Bell, Stuart J. Rowan, Osvaldo Gutierrez and Matthew R. Golder*, ","doi":"10.1021/jacs.4c04401","DOIUrl":null,"url":null,"abstract":"<p >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.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacs.4c04401","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
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.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.