Bent π-conjugated systems composed of three-dimensional benzoannulenes

This article describes bent π-conjugated systems composed of alternating o-phenylene and Z-vinylene units. all-Z-[n]Benzo[4n]annulenes are higher homologues of dibenzocyclooctatetraene (DBCOT) with a concave π system, and attempts were made to convert [20]- and [24]annulenes having partial belt structures of fullerenes and carbon nanotubes into [10]- and [12]phenacenes. A bent π-conjugated system composed of two DBCOT units showed dynamic syn-anti equilibrium in solution and behaved as dynamic molecular tweezers (DMTs). The syn isomers of the DMTs formed blue charge-transfer complexes with DDQ in solution, and this complexation and color change were applied to thermochromism. Furthermore, DMTs having two CN groups on each COT ring exhibited crystalline-state emission in the presence of solvent molecules, although almost no emission was observed in solution or the solid state. Based on this crystalline-state emission, a vapochromic system was established. The multifunctional properties of DMTs caused by the flexibility of the nonplanar π system are summarized.