The synthesis and properties of dinaphtho[1,8-bc:1′,8′-ef ]thiepine bisimide (DNTBI) and its oxides are described. Their molecular design is conceptually based on the insertion of a sulfur atom into the perylene bisimide (PBI) core. These sulfurinserted PBI derivatives adopt nonplanar structures, which significantly increases their solubility in common organic solvents. Upon electron injection, light irradiation, or heating, DNTBI and its sulfoxides undergo sulfur extrusion reactions to furnish PBI. The photoinduced and thermal sulfur extrusion reactions proceed almost quantitatively. This unique reactivity enabled the fabrication of a high-performance solution-processed n-type organic field-effect transistor with an electron mobility of up to 0.41 cm 2 V −1 s −1 .

Establishing design principles to create nonplanar π-conjugated molecules is crucial for the development of novel functional materials. Herein, we describe the synthesis and properties of dinaphtho­[1,8-bc:1′,8′-ef]­azepine bisimides (DNABIs). Their molecular design is conceptually based on the insertion of a nitrogen atom into a perylene bisimide core. We have synthesized several DNABI derivatives with a hydrogen atom, a primary alkyl group, or an aryl group on the central nitrogen atom. These DNABIs exhibit nonplanar conformations, flexible structural changes, and ambipolar redox activity. The steric effect around the central nitrogen atom substantially affects the overall structures and results in two different conformations: a nonsymmetric bent conformation and a symmetric twisted conformation, accompanied by a drastic change in electronic properties. Notably, the nonsymmetric DNABI undergoes unique structural changes in response to the application of an external electric field, which is due to molecular motions that are accompanied by an orientational fluctuation of the dipole moment. Furthermore, the addition of a chiral Brønsted base to N-unsubstituted DNABI affords control over the helical chirality via hydrogen-bonding interactions.