Mechanochemical Reactivity of a 1,2,4-Triazoline-3,5-dione-Anthracene Diels-Alder Adduct

Force-responsive molecules that produce fluorescent moieties under stress provide a means for stress-sensing and material damage assessment. In this work, we report a mechanophore based on Diels-Alder adduct TAD-An of 4,4′-(4,4′-diphenylmethylene)-bis-(1,2,4-triazoline-3,5-dione) and initiator-substituted anthracene that can undergo retro-Diels-Alder (rDA) reaction by pulsed ultrasonication and compressive activation in bulk materials. The influence of having C−N versus C−C bonds at the sites of bond scission is elucidated by comparing the relative mechanical strength of TAD-An to another Diels-Alder adduct MAL-An obtained from maleimide and anthracene. The susceptibility to undergo rDa reaction correlates well with bond energy, such that C−N bond containing TAD-An degrades faster C−C bond containing MAL-An because C−N bond is weaker than C−C bond. Specifically, the results from polymer degradation kinetics under pulsed ultrasonication shows that polymer containing TAD-An has a rate constant of 1.59×10⁻⁵ min⁻¹, while MAL-An (C−C bond) has a rate constant of 1.40×10⁻⁵ min⁻¹. Incorporation of TAD-An in a crosslinked polymer network demonstrates the feasibility to utilize TAD-An as an alternative force-responsive probe to visualize mechanical damage where fluorescence can be “turned-on” due to force-accelerated retro-Diels-Alder reaction.