Computational DFT data afforded the dissociation energy (Ediss) for a series of anthracene-derivatives to be exploited as EPOs. Starting from a set of known molecules, three anthracene derivatives were selected as suitable candidates according the calculated values of Ediss. DIPA, PCPA, and PFPA were prepared by addition of alkynyl and/or aromatic substituents in positions 9 and 10 of the anthracene scaffold and the crystallographic analysis of these structures confirmed the favorable orientation of the appended moieties to accommodate the EPO bridges.