Further evidence for spontaneous solid-state polymerisation reactions in 2,5-dibromothiophene derivativesElectronic supplementary information (ESI) available: X-ray data for DBMDTT, DBEDTT and DBPDTT. See http://www.rsc.org/suppdata/jm/b3/b307575n/

Three new, highly crystalline 2,5-dibromothiophene compounds polymerise on standing in the absence of solvent and catalyst; X-ray crystallography shows that the molecules are held in close proximity by several short intermolecular contacts, facilitating the coupling of monomers.