A backbone lever-arm effect enhances polymer mechanochemistry.
Mechanical forces along a polymer backbone can be used to bring about remarkable reactivity in embedded mechanically active functional groups, but little attention has been paid to how a given polymer backbone delivers that force to the reactant. Here, single-molecule force spectroscopy was used to directly quantify and compare the forces associated with the ring opening of gem-dibromo and gem-dichlorocyclopropanes affixed along the backbone of cis-polynorbornene and cis-polybutadiene. The critical force for isomerization drops by about one-third in the polynorbornene scaffold relative to polybutadiene. The root of the effect lies in more efficient chemomechanical coupling through the polynorbornene backbone, which acts as a phenomenological lever with greater mechanical advantage than polybutadiene. The experimental results are supported computationally and provide the foundation for a new strategy by which to engineer mechanochemical reactivity.
Duke Scholars
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- Spectrum Analysis
- Plastics
- Organic Chemistry
- Molecular Structure
- Mechanics
- Elastomers
- Computer Simulation
- Butadienes
- 34 Chemical sciences
- 03 Chemical Sciences
Citation
Published In
DOI
EISSN
ISSN
Publication Date
Volume
Issue
Start / End Page
Related Subject Headings
- Spectrum Analysis
- Plastics
- Organic Chemistry
- Molecular Structure
- Mechanics
- Elastomers
- Computer Simulation
- Butadienes
- 34 Chemical sciences
- 03 Chemical Sciences