Tetraazatetraoxodecacene and tetraazatetrathiodecacene: Synthesis, crystal structures, linear and third-order nonlinear optical properties

In this manuscript, the longest O/N and S/N atoms containing heteroacenes (tetraazatetraoxodecacene (TAOD) and tetraazatetrathiodecacene (TATD)) with ten linearly fused rings have been synthesized and fully characterized. The X-ray crystal structures show that O/N atoms containing TAOD exhibits a linear structure, while S/N atoms containing TATD bends in S atom containing heterorings. Obviously, TAOD shows a higher fluorescence quantum yield in solution than that of S atom containing compound TATD. By simple reprecipitation method, TAOD and TATD self-assembly into different microstructures with microwires and microrods, respectively, which demonstrate distinctive non-linear optical properties depending on the orientation of transition dipoles.