Electrochemical studies of a new, low-band gap inherently chiral ethylenedioxythiophene-based oligothiophene

In the present paper, the synthesis and characterization of 2,2′-bis{bi[2,2’-(3,4-ethylenedioxy)thiophen-5-yl]}-3,3′-bithianaphthene, nicknamed BT2E4, is reported. We show that electrooligomerization of BT2E4 leads to electroactive films which are evaluated by cyclic voltammetry (CV), UV/vis spectroelectrochemistry and CV coupled with in-situ conductance measurements. Direct comparisons to the properties of the oligomers obtained from the atropisomeric all-thiophene analogue BT2T4 show that the introduction of EDOT leads to a strong reduction of the band-gap, an overall red-shifted absorption spectrum and a rigidification of the structure. Finally, DFT and TD-DFT calculations were performed in parallel to investigate and to compare the electronic and molecular structures of neutral and charged monomer and oligomer species.