Data from: Distal conformational locks guide reaction pathways for enhanced metallocene mechanochemistry

• 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

6 files (3.88 MB)

Data Citation

• Zhang, Y., Wang, Z., Kouznetsova, T., Sha, Y., Xu, E., Shannahan, L., … Craig, S. (2020). Data from: Distal conformational locks guide reaction pathways for enhanced metallocene mechanochemistry. Duke Research Data Repository. https://doi.org/10.7924/r4kw5cx8q

Creator

• Sha, Ye
• Tang, Chuanbing
• Fermen-Coker, Muge
• Xu, Enhua
• Zhang, Yudi
• Craig, Stephen
• Shannahan, Logan
• Kouznetsova, Tatiana
• Wang, Zi

DOI

• 10.7924/r4kw5cx8q

Subject

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

Publication Date

• January 16, 2020

ARK

• ark:/87924/r4kw5cx8q

Is Replaced By

• 10.7924/r4125x84n

Affiliation

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

Publisher

• Duke Research Data Repository

Language

• English

Type

• Dataset

Format

• TXT
• RTF
• PDF

Funding Agency

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

Grant Number

• CHE-1904016
• W911NF-15-0143

Contact

• Stephen Craig: stephen.craig@duke.edu, ORCID: 0000-0002-8810-0369

License

• Creative Commons CC0 1.0 Universal

Title

• Data from: Distal conformational locks guide reaction pathways for enhanced metallocene mechanochemistry

License

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

Repository

• Duke Research Data Repository

• Files
• Readme

Thumbnail	Title	Date Uploaded	Visibility	Actions
	README.txt	2020-01-16	Public	Download
	figure 2c-cis3fcp.rtf	2020-01-16	Public	Download
	figure 2c-cis5fcp.rtf	2020-01-16	Public	Download
	figure 2c-fc.rtf	2020-01-16	Public	Download
	figure 2c-trans3fcp.rtf	2020-01-16	Public	Download
	Supplementary Information.pdf	2020-01-16	Public	Download

View as Markdown View as Text

Versions