Organic Chemistry

Mechanical Force Enables an Anomalous Dual Ring-Opening Re-action of Naphthodipyran

Authors

Abstract

Multimodal mechanophores that exhibit complex mechanochromic behavior beyond the typical binary response are capable of distinguishing between multiple stress states through discrete changes in color. Naphthodipyran photoswitches contain two pyran rings fused to a central naphthalene core and represent a potentially promising framework for multimodal reactivity. However, the concurrent ring opening of both pyran moieties has previously proven inaccessible via photochemical activation. Here, we demonstrate that mechanical force supplied to naphthodipyran through covalently bound polymer chains generates the elusive dual ring-opened dimerocyanine product with unique near-infrared absorption properties. Trapping with boron trifluoride renders the merocyanine dyes thermally persistent and reveals unusual sequential ring-opening behavior that departs from the reactivity of previously studied mechanophores under the high strain rates imposed by ultrasound-induced solvodynamic chain extension.

Content

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Supplementary material

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Supporting Information
Experimental details, synthetic procedures, DFT calculations, GPC chromatograms, UV-vis absorption and mass spectrometry data, and NMR spectra.