Supramolecular Polymerization of a Photo-Fluttering Chiral Monomer: A Temporarily Suspendable Chain Growth by Light

Using a photochemically fluttering thiophene-fused cyclooctatetraene derivative (COT) as a nonplanar chiral monomer, we have succeeded in remotely suspending the supramolecular polymerization in a temporal manner by a completely new strategy. The COT monomer with an 8π electron core adopts a saddle shape in the ground state and flutters 5.8 × 10³ times faster upon photoirradiation than in the dark as a result of the stabilized planar conformation by the excited-state aromaticity (Baird aromaticity). Detailed investigation revealed that without photoirradiation the rate constant of the fluttering motion is 1/560 times smaller than that of the chain elongation, indicating that the fluttering of COT does not affect the chain elongation in the dark. In contrast, under photoirradiation (365 nm), the fluttering of COT is at least 11 times more rapid than the chain elongation, thereby suppressing the elongation event. The rapid fluttering of COT to suspend the chain elongation is not accompanied by a decrease in active monomer concentration, leading to depolymerization.