Tetrathia[22]annulene[2,1,2,1] and its derivatives are p-type organic semiconductors possessing relatively high mobilities in thin film field-effect transistors. To get a full understanding of the relationship between the molecular structures and transporting properties of these macrocyclic molecules, the single crystal structures of three meso-substituted tetrathia[22]annulene[2,1,2,1]s were determined by X-ray diffraction, and the electrical properties were investigated by single crystal transistor characterization and quantum simulations. The observed relationship between the mobilities of different crystals was strongly corroborated by calculations of both the molecular reorganization energies and the maximum intermolecular transfer integrals.

Fullerene/sulfur-bridged annulene cocrystals with a two-dimensional segregated alternating layer structure were prepared by a simple solution process. Single-crystal analysis revealed the existence of continuing π–π interactions in both the donor and acceptor layers, which serve as transport paths for holes and electrons separately. The ambipolar transport behaviors were demonstrated with single-crystal field-effect transistors and rationalized by quantum calculations. Meanwhile, preliminary photoresponsivity was observed with the transistor configuration.

Tetrathia[22]annulene[2,1,2,1] and its derivatives are p-type organic semiconductors possessing relatively high mobilities in thin film field-effect transistors. To get a full understanding of the relationship between the molecular structures and transporting properties of these macrocyclic molecules, the single crystal structures of three meso-substituted tetrathia[22]annulene[2,1,2,1]s were determined by X-ray diffraction, and the electrical properties were investigated by single crystal transistor characterization and quantum simulations. The observed relationship between the mobilities of different crystals was strongly corroborated by calculations of both the molecular reorganization energies and the maximum intermolecular transfer integrals.