We describe the preparation of two monomers that bear complementary nucleobases at the edges (guanine-2′-deoxycytidine and 2- aminoadenine-2′-deoxyuridine) and that are conveniently protected and activated for solid-phase automated DNA synthesis. We report the optimized synthetic routes leading to the four nucleobase derivatives involved, their crosscoupling reactions into dinucleobase-containing monomers, and their oligomerization in the DNA synthesizerFunding from the European Research Council (ERC-Starting Grant 279548 PROGRAM-NANO) and MINECO (CTQ2014-57729-P, SAF2017-87305-R and CTQ2017- 84727-P) is gratefully acknowledge
