Synthesis and crystal structure of 5,12-diphenyl-6,11-bis(thien-2-yl)tetracene

5,12-Diphenyl-6,11-bis(thien-2-yl)tetracene (1) was prepared by reduction of 5,12-diphenyl-6,11-bis(thien-2-yl)-6,11-tetracenediol (3) with NaBH3CN in the presence of weak Lewis acid ZnI2. A rearranged byproduct, 6,11-dihydro-5,12-diphenyl-6,6′-bis(thien-2-yl)-11,11′-dihydrotetracene (5), was also obtained under this condition. Treatment of compound 3 with HI or other strong Lewis acid led to rearrangement and afforded 5,12-diphenyl-6,6′-bis(thien-2-yl)tetracene-11-one (4). The structures of compounds 1, 4 and 5 were confirmed by single crystal X-ray diffraction. The central tetracene rings of molecules 1 are twisted and assemble into arrays with slip parallel molecules in the crystal structure. There is no π–π overlap among the tetracene rings or among the pendant phenyl rings and thienyl rings.