Trichalcogenasumanene ortho-Quinones: Synthesis, Properties, and Transformation into Various Heteropolycycles

The regioselective transformation of heterobuckybowl trichalcogenasumanenes 1 a,b at peripheral butoxy groups afforded trichalcogenasumanene ortho-quinones 2 a,b. Compounds 2 a,b are distinct from 1 a,b in terms of their molecular geometry and electronic state; that is, they have a shallower bowl depth and show absorbance in the NIR region. The reaction of 2 a,b with diamines resulted in a variety of heteropolycycles, including molecular spoon 3 a-6a, planar pi-systems 3 b-6b, and highly twisted [7-6-6]-fused systems 7 a,b. These new heteropolycycles had different optical/electrical properties: 4 a,b showed hole mobility of approximately 0.002cm(2)V(-1)s(-1), 6a displayed red emission in both solution and the solid state, and 7 a,b formed tight stacks of the curved pi-surface.