Fullerene fragments, referred to as buckybowls, are garnering interest due to their distinctive molecular shapes and optoelectronic properties. Here, we report the synthesis and characterization of a novel C subunit, diindeno[4,3,2,1-:4',3',2',1'-]perylene, that is substituted with either triethylsilyl(TES)-ethynyl or 2,4,6-triisopropylphenyl groups at the -positions. The resulting compounds ( and ) display a bowl-to-bowl inversion at room temperature. Notably, the substituent groups on the -positions alter both the geometric and the electronic properties as well as the crystal packing of the buckybowls. In contrast to the 2,4,6-triisopropylphenyl groups in , the TES-ethynyl groups in lead to enhanced bond length alternation, resulting in weaker aromaticity of the six-membered rings of the buckybowl skeleton. forms one-dimensional (1D) concave-in-convex stacking columns, and when is blended with C, the buckybowls encapsulate C and result in two-dimensional cocrystals. Organic field-effect transistor (OFET) measurements demonstrate that displays a hole mobility of 0.31 cm V s, and the -C cocrystal exhibits ambipolar transport characteristics with electron and hole mobilities approaching 0.40 and 0.07 cm V s, respectively. This work demonstrates the potential of buckybowls for the development of organic semiconductors.