Synthesis Of All Thiophene-Based [7]Helicenes And Trithienothiepines With Isomeric Location Of Sulfur Atoms Based On Intramolecular Selectivity Of Deprotonation

Three unsymmetric thiophene-based [7]helicenes, namely, endo-exo-UH-1, endo-top-UH-2, and exo-top-UH-3, with different isomeric locations of sulfur atoms in two terminal thiophene rings were efficiently synthesized using di thi eno [2,3-b:3',2'-d] - thiophen e (bb-DTT), dithieno [2,3- b:2',3'-d] thiophene (bt-DTT), and dithieno[2,3-b:3',4'-d]thiophene (bs-DTT) as building blocks via Suzuki cross-coupling and intramolecular cyclization reactions. Aside from these racemic [7]helicenes, two novel heterocyclic isomers, namely, trithienothiepines TTTP-1 and TTTP-2, were simultaneously obtained during the intramolecular cyclization. Two novel deprotonations of bi-DTTs and cyclization for synthesizing target compounds showed high selectivity and efficiently constructed both UHs and TTTPs. X-ray crystallographic analyses revealed that the UHs have typical helical molecular structures. The isomeric location of sulfur atoms in the two terminal thiophene rings in endo-exo-UH-1, endo-top-UH-2, exo-top-UH-3, and TTTP-1 allowed multiple intermolecular interactions, such as S center dot center dot center dot S, S center dot center dot center dot C, and S center dot center dot center dot H interactions, resulting in different crystal-packing patterns. Moreover, the absorption behaviors of these [7]helicenes, TTTP-1, and TTTP-2 were examined and theoretically calculated. Results indicated that the isomeric location of sulfur atoms plays a key role in tuning intramolecular pi-electronic conjugation.