Donor-acceptor-donor arrays based on an anthracene bisimide (ABI) skeleton appended with 6,13-diethynylpentacene and 9,10-diethynylanthracene units have been constructed by Sonogashira coupling followed by reductive aromatization. Their photophysical and electrochemical properties are compared with those of the corresponding mono-substituted analogs on the basis of theoretical calculations and cyclic voltammetry to evaluate the intramolecular electronic interactions between ABI as the acceptor unit and diethynylacene as the donor unit.