The mechanochemical activation of a pyrimidine dimer

Abstract

The cyclobutane motif is a versatile force-reactive moiety enabling diverse mechanophores and their associated functions in polymer mechanochemistry. For example, the cyclobutane core has been applied in the context of stress-responsive polymers, self-healing materials, and self-sensing nanocomposites. However, leveraging the cyclobutane structure for the development of nucleobase- and nucleoside-derived mechanophores remains unexplored. Here, we introduce a pyrimidine dimer mechanophore based on a cyclobutane core (CPD), formed via photoinduced [2 + 2] cycloaddition of thymine under ultraviolet B (UVB) irradiation. Upon ultrasound exposure, the polymer-centered CPD undergoes formal cycloelimination. To better understand the individual mechanochemical contributions of the four possible CPD stereoisomers upon force input, we employ the CoGEF and FM-PES methods and compare the results. Experimental and computational methods suggest that the syn-diastereomers cleave preferentially compared to their anti-counterparts under mechanical force.