This research demonstrates concerted 1,3-sigmatropic rearrangements enabling spin-state control in methylenecyclopropane and trimethylenemethane.
The reversible interconversion between methylenecyclopropane (MCP) and trimethylenemethane (TMM) has been extensively studied, yet precise control over their spin states remains challenging. Here, we designed and synthesized a propeller-shaped π-extended MCP derivative and its corresponding TMM derivative with anthroxyl moieties. The MCP derivative was isolated as a stable compound, and upon photoirradiation, it generated the triplet-state TMM derivative, which reverted to MCP derivative without decomposition. In contrast, thermal excitation induced a unique carbon-carbon bond fluxionality within the MCP core via a concerted 1,3-sigmatropic rearrangement rather than a stepwise diradical pathway. These findings demonstrate that external stimuli such as light and heat enable spin-state control and dynamic bond fluxionality, providing new insights into organic stimuli-responsive materials.
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Konrai et al. (2025) studied this question.
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