Guanine (G) rich G(4)T(4)G(4) DNA and homologous PNA strands tend to form antiparallel dimeric quadruplexes. In contrast, the same DNA strands carrying planar aromatic 5'-residues preferentially form parallel DNA quadruplex. Conformation and composition of the DNA quadruplexes can be programed by pi-pi-stacking interaction exerted by the 5'-residues.