A new small molecule, with D-A-D framework was prepared in good yield by using a [2+1+2+1] cycloaddition followed by the [4+2] Diels–Alders reaction. Additionally, tetra-substituted naphthalene derivatives were also prepared from in situ generated benzyne (using 2-trimethylsilylphenyl triflate and cesium fluoride). All of this compounds exhibit strong 2D-π-conjugation. The influence of this type of interactions on photophysical properties with the aid of DFT calculations was examined. The preliminary tests of application possibility of synthesized compounds in devices for optoelectronics were carried out as well.