The title imides possessing a planar acenaphthofluoranthene moiety were prepared by the Diels-Alder reaction of diacenaphtho[1,2-b:1',2'-d]thiophene and maleic anhydride and subsequent treatment with amines. The reaction with maleimide afforded the corresponding 1:2 adduct displaying intense blue fluorescence in solution. Although the imides crystallize yellow needles, their amorphous solids are red. Concentration-dependent (HNMR)-H-1 spectra of a N-octyl derivative reveal self-aggregation behavior in CDCl3.