The Synthesis,Functionalization And Supramolecular Self-Assembly Of Trithiasumanene And Triselenasumanene

The curved structures of carbon-rich materials(such as fullerenes and carbon nanotubes)exhibit unique properties which attach great interests in many fields.As the fragment of fullerenes,the novel structures of bowl-shaped polycyclic aromatic hydrocarbons(known as buckybowls or bowlenes)give bowlenes unique electronic properties,for example,asymmetrically polarized electron cloud and electronic-rich surface,which provide bowlenes potentials in supramolecular materials,liquid crystal and organic semiconductors.However,the research of heterasumanenes is relatively rare.The inclusion of heteroatoms is able to change the electronic structure of bowlenes from relatively electron-deficient to electron-rich,and thus heterasumanenes could be potential in superconductor,organic photovoltaics and organic electronics.The most typical heterasumanenes is trithiasumanene,which is the first successfully synthesized heterasumanens.Trithiasumanene contains three thiophene rings and four benzene rings,in which the lone electron pairs of sulfur atoms enhance the electron-donating ability of trithiasumanene.Due to the high chemical reactivity,halogens on aromatic rings can be substituted by other functional groups,which can tune the physicochemical properties of aromatic hydrocarbons.Therefore,halogenated aromatic hydrocarbons are crucial precursors in functionalization.Similarly,in order to modulate the physicochemical properties of trithiasumanene,we tried to the bromination on the edge of trithiasumanene,and the sequential thiolation of brominated trithiasumanene.Taking advantage of electron-rich structures of trithiasumanene and triselenasumanene,which were able to assemble with fullerene form concave-convex complex.The charge transfer between bowlenes and fullerenes was observed.Their supramolecular complexes show high stability and strong ?-? interactions.The supramolecular complexes could be useful in organic electronics.