Data from: Distal conformational locks on ferrocene mechanophores guide reaction pathways for increased mechanochemical reactivity

• When incorporated into polymeric materials, mechanophores can be used to produce strain-dependent covalent chemical responses, including stress-strengthening, stress-sensing and network remodeling. In general, it is desirable for mechanophores to be highly inert in the absence of force but highly reactive under applied tension. Metallocenes possess remarkable combinations of force-free stability and force-coupled reactivity, but the mechanistic basis of this reactivity remains largely unexplored. Here, we use single molecule force spectroscopy to probe the mechanical reactivity of a series of ferrocenophanes and elucidate the mechanistic factors that dictate their mechanochemical activity. The force-coupled rate of cyclopentadiene (Cp) dissociation among various ferrocene derivatives varies by several orders of magnitude at ~1 nN, and the differences in reactivity are not correlated with ring strain in the reactants, but the extent of rotational realignment of the two Cp ligands. Mechanophores with pulling points that are conformationally restricted by distal attachments to an eclipsing orientation are most labile, whereas conformationally unrestricted ligands reorient under force to effectively superpose "catch bond" like contributions onto the overall mechanically assisted dissociation reaction. The ability to program the mechanism of ferrocene dissociation to proceed through ligand "peeling", as opposed to the more conventional "shearing" mechanism of the parent ferrocene, leads to enhanced macroscopic, multi-responsive behavior including mechanochromism and force-induced crosslinking in ferrocenophane-containing polymers. ... [Read More]

Total Size

10 files (4.51 MB)

Data Citation

• Zhang, Y., Wang, Z., Kouznetsova, T., Sha, Y., Xu, E., Shannahan, L., Fermen-Coker, M., Lin., Y. (2020). Data from: Distal conformational locks on ferrocene mechanophores guide reaction pathways for increased mechanochemical reactivity. V3 Duke Research Data Repository. https://doi.org/10.7924/r4gq6z428

Creator

• Tang, Chuanbing
• Lin, Yangju
• Xu, Enhua
• Shannahan, Logan
• Wang, Zi
• Fermen-Coker, Müge
• Sha, Ye
• Zhang, Yudi
• Kouznetsova, Tatiana

DOI

• 10.7924/r4gq6z428

Subject

• Metallocene
• Polymer chemistry
• Chemistry, Physical and theoretical
• Mechanical chemistry
• Chemistry, Organic

Publication Date

• October 28, 2020

ARK

• ark:/87924/r4gq6z428

Replaces

• 10.7924/r4125x84n

Affiliation

• University of South Carolina. Department of Chemistry
• Graduate School of System Informatics, Kobe University, Kobe 657-8501, Japan
• College of Science, Nanjing Forestry University, Nanjing, 210037, China
• U.S. Army Research Laboratory
• Chemistry

Publisher

• Duke Research Data Repository

Language

• English

Type

• Dataset

Format

• PDF
• CSV
• RTF
• TXT

Related Materials

• Zhang, Y., Wang, Z., Kouznetsova, T.B. et al. Distal conformational locks on ferrocene mechanophores guide reaction pathways for increased mechanochemical reactivity. Nat. Chem. 13, 56–62 (2021).  https://doi.org/10.1038/s41557-020-00600-2

Provenance

• Version 3 adds additional raw data files and an updated Supplemental Information file.

Funding Agency

• U.S. Army Research Laboratory and the Army Research Office
• National Science Foundation

Grant Number

• CHE-1904016
• W911NF-15-0143

Contact

• Stephen Craig: stephen.craig@duke.edu

License

• Creative Commons CC0 1.0 Universal

Title

• Data from: Distal conformational locks on ferrocene mechanophores guide reaction pathways for increased mechanochemical reactivity

License

• http://creativecommons.org/publicdomain/zero/1.0/

Repository

• Duke Research Data Repository

Versions

Version	DOI	Comment	Publication Date
3	10.7924/r4gq6z428	Version 3 adds additional raw data files and an updated Supplemental Information file.	2020-10-28
2	10.7924/r4125x84n	Version 2 is published with an updated title and author list, replaces existing supplemental information with updated file.	2020-09-08
1	10.7924/r4kw5cx8q		2020-01-16