Alternated quinoid/aromatic units in terthiophenes building blocks for electroactive narrow band gap polymers....

We report here the synthesis of three novel pi-conjugated heterocyclic mixed trimers that contain two electron-donating 3,4-ethylenedioxy-2-thienyl (EDOT) units covalently attached to a central proquinoid electron-accepting thienopyrazine moiety (two of these narrow-HOMO-LUMO gap D-A-D compounds also bear hexyl side chains attached either to the outermost alpha positions of the EDOT end rings or to the beta positions of the pyrazine fused ring). The modification of the terthiophene structure upon EDO, pyrazine, and hexyl substitutions has been treated in detail with spectroscopic and theoretical arguments. Solid-state properties reveal the occurrence of short intramolecular contacts between heteroatoms of adjacent rings. The analysis of the structure of the pi-conjugated backbone of each molecule is consistent with a partial quinoid-like pattern which partially reverts to be subtly more aromatic depending on the topology of the positive inductive effect of the hexyl chains. This quinoidization is a consequence of the appearance of a D(EDOT)-->A(PyT)<--D(EDOT) intramolecular charge transfer which further polarizes the structure. The same chemical concepts have been applied to address their electrochemical behavior. The three mixed trimers exhibit amphoteric properties due to the combination of electron acceptor and donor groups. Given their relative low HOMO-LUMO energy gap, these trimers promise to be good candidates for obtaining polymers with significant low energy gap combining electroactivity.