Incorporation of a Tethered Alcohol Enables Efficient Mechanically Triggered Release in Aprotic Environments

Abstract

Polymers that release small molecules in response to mechanical force are promising for a wide variety of applications. While offering a general platform for mechanically triggered release, previous mechanophore designs based on masked 2-furylcarbinol derivatives are limited to polar protic solvent environments for efficient release of the chemical payload. Here, we report a masked furfuryl carbonate mechanophore incorporating a tethered primary alcohol that enables efficient release of a hydroxycoumarin cargo in the absence of a protic solvent. Density functional calculations also implicate an intramolecular hydrogen bonding interaction between the tethered alcohol and the carbonyl oxygen of the carbonate that reduces the activation barrier for carbonate fragmentation leading to molecular release. This new mechanophore design expands the generality of the masked 2-furylcarbinol platform for mechanically triggered release, enabling the implementation of this strategy in a wider range of chemical environments.