Mechanochemistry of Cationic Cobaltocenium Mechanophore.

Journal Article (Journal Article)

Recent research on the mechanochemistry of metallocene mechanophores has shed light on the force-responsiveness of these thermally and chemically stable organometallic compounds. In this work, we report a combination of experimental and computational studies on the mechanochemistry of main-chain cobaltocenium-containing polymers. Ester derivatives of the cationic cobaltocenium, though isoelectronic to neutral ferrocene, are unstable in the nonmechanical control experimental conditions that were accommodated by their ferrocene analogs. Replacing the electron withdrawing C-ester linkages with electron-donating C-alkyls conferred the necessary stability and enabled the mechanochemistry of the cobaltocenium to be assessed. Despite their high bond dissociation energy, cobaltocenium mechanophores are found to be selective sites of main chain scission under sonomechanical activation. Computational CoGEF calculations suggest that the presence of a counterion to cobaltocenium plays a vital role by promoting a peeling mechanism of dissociation in conjunction with the initial slipping.

Full Text

Duke Authors

Cited Authors

  • Cha, Y; Zhu, T; Sha, Y; Lin, H; Hwang, J; Seraydarian, M; Craig, SL; Tang, C

Published Date

  • August 2021

Published In

Volume / Issue

  • 143 / 30

Start / End Page

  • 11871 - 11878

PubMed ID

  • 34283587

Electronic International Standard Serial Number (EISSN)

  • 1520-5126

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/jacs.1c05233


  • eng