Synthesis, Structures, and Physical Properties of ExTTF Substituted with Aryl Groups through Sulfur Bridges and the Electron Transfers with C60

ExTTF derivatives (1–4) bearing aryl groups attached through sulfur bridges have been synthesized. The peripheral aryl groups have a certain influence on both the electronic and crystallographic properties of the exTTFs. Compounds 1–4 show two bands typical of exTTF derivatives near 360 and 430 nm. Compound 1 and 4 exhibit the characteristic electrochemical exTTF behavior, with one reversible two‐electron process ranging depending on their substitution the electron‐withdrawing ability. But 2 and 3 exhibit a similar single two‐electron oxidation wave but electrochemically irreversible redox with peak‐to‐peak potential separation. And 3 has a low redox potential, which is significantly inconsistent with the electron absorption of pyridine substituents. The crystal structures of 1–4 exhibit the characteristic butterfly shape. Moreover, the peripheral aryl groups exhibit multiple alignment modes with respect to the central exTTF core, caused by their rotation about the two C−S bonds of the sulfur bridges. Under the interaction of multiple molecules, exTTF shows different molecular packing structures. Compounds 1–4 have charge transfer with C₆₀ due to their good electron‐donating ability, butterfly configuration, and free rotation of peripheral aryl groups. These results indicate that 1–4 organic electronic materials have potential applications in the field of supramolecular assembly.