Preparation of enediyne-crosslinked networks and their reactivity under thermal and mechanical conditions

Abstract

The COGEF technique (COnstrained Geometries simulating External Force) was used to investigate the effects of macroscopic forces on cyclic enediynes, which can undergo Bergman Cyclization (BC). Because the forces needed to activate BC were found to be less than the forces needed for chain scission in polymer backbones, the calculations suggest that enediynes are potentially useful mechanophores. Three enediynes studied computationally were synthesized. The thermal BC reactions for these compounds were studied by DSC and found to be consistent with the predicted thermal sensitivity based on known substituent effects. However, upon incorporation of the enediynes into a polymer matrix as crosslinks, no definitive mechanical activation was observed, and conclusions about the stress-sensitivity of enediynes were unable to be drawn. Model studies suggest that insufficient force was applied to the crosslinks for mechanical activation to be observable by DSC.