Effect of Annulation Mode of Twistarene on the Physical Property and Self‐Assembly Behavior of Functionalized Curved Aromatic Molecules

Four novel curved polycyclic aromatic hydrocarbons 3 a, 5, 8, 15 a have been synthesized and characterized, where molecules 3 a and 15 a bear [5]carbohelicene units. X‐ray single crystal analyses indicate that compound 3 a shows offset packing arrangements of (P5)‐ and (M5)‐isomers, and 15 a has a symmetrical plane and looks like a butterfly. In comparison, 8 exhibits a slightly curved structure, in which the significant convex‐to‐convex π‐overlap with the shortest distance of 3.42 Å occurs. In addition, the effect of annulation mode of twistarenes on the physical properties, self‐assembly behaviors, and switchable photoconductivity of the as‐prepared curved aromatic compounds were further examined in a comparative manner. Constructing novel curved polycyclic aromatic hydrocarbons is of great significance. Herein this work describes the design and modular preparation of four novel arenes where their structures are determined via X‐ray diffraction analyses. The effect of annulation mode of twistarenes on the physical properties, self‐assembly behaviors and switchable photoconductivity of such curved molecules were investigated in detail.