The photoluminescence (PL) frequencies and quantum efficiencies of dithieno[3,2-
b;2',3'-
d]thiophene-4,4-dioxide (
1), its 3,5-dimethyl derivative (
2), and the corresponding 4-oxide(
3) are reported and discussed in relation to their single-crystal X-ray structures. The peculiarpacking modalities of dioxides
1 and
2, based on dimeric units originated by short S···Ocontacts between molecules related by an inversion center, cause an unusually highbathocromic shift of PL frequencies from solution to solid state. This effect is accompaniedby a marked decrease in solid-state PL efficiencies (12% and 16%) compared to those insolution (75% and 77%). In monoxide
3 the loss of local symmetry inherent to the changeSO
2 SO deeply modifies the self-assembly and PL properties, and the PL efficiency in thesolid state is close to that in solution. Ab initio calculations on the ground and excited statesof compound
1 were performed and compared to those of a conformationally mobilecounterpart. Oligomers containing dithienothiophene
2 as internal core were synthesizedand found to be characterized by high PL efficiencies in the solid-state (up to 48%) as wellas in solution (up to 85%). The current-voltage and luminance-voltage plots of anelectroluminescent diode fabricated with one of these new rigid-core oligothiophene-
S,
S-dioxides are reported.