The reaction of 1,5-dibromoanthracene with butyllithium and diethyloxalate followed by saponification gives anthrylene- 1,5-diglyoxylic acid as a bifunctional reactant. Its double condensation with 2-bromophenylacetic acid, followed by double cyclization, leads to a bright-orange nearlinear dinaphtho-anthracene-tetracarboxdiimide with substituents on the naphthalene moieties. An analogous condensation-cyclization sequence of 2,5-dibromophenylene-1,4- diacetic acid with 1-naphthylglyoxylic acid leads to an iso-meric red diimide substituted on the anthracene nucleus. The striking difference in band gaps shows that diimide substitution on the central moiety of diareno[a,h]anthracenes is particularly efficient in inducing long-wavelength absorption. The substitution dependence of the band gap is found to be mainly caused by a variation of the reduction potentials with substituent position, whereas the oxidation potentials are largely substitution-independent.