Synthesis of Three‐Dimensional Butterfly Slit‐Cyclobisazaanthracenes and Hydrazinobisanthenes through One‐Step Cyclodimerization and Their Properties

Abstract New three‐dimensional (3D) π‐conjugated molecules, butterfly‐shaped slit‐cyclobisazaanthracenes, were synthesized in high yields by Ni‐mediated one‐step cyclodimerization of dibromoazaanthracenes with a dimethylacridine, phenothiazine, or acridone skeleton. The 3D slit butterfly shape was formed by folded azaanthracene skeletons. Closure of the slit via NN bond formation afforded hydrazinobisanthenes with an embedded hydrazine structure in a bisanthene skeleton, which exhibited a 3D butterfly or a 2D plane structure depending on the type of heterocycle used. Extensive study of the stereoselective chemical reactivity of the butterfly shape, X‐ray analysis, DFT calculations, electrochemical/chemical oxidations, and photophysical measurements revealed that the properties of these materials included stereoselective oxidation, a rigid or flexible butterfly shape, dynamic conformational behavior, unique crystal‐packing structures, excellent electron donation with low oxidation potential, a radical cation, a long absorption wavelength, and fluorescence property.