This PhD was focused in the reactivity and the study of (chir)optical properties of DMQA and DAOTA scaffolds, and their derivatives. The late stage functionalization of the [4]helicene core by electrophilic aromatic substitution reactions and derivatization, provided a substrate scope of 26 derivatives, and includes the solid state analysis, electronic, absorption and emission properties of these compounds, and for some enantiopure adducts, the study of the electronic circular dichroism and circularly polarized luminescence. The solid state analysis, electronic, absorption and emission properties upon the introduction of the auxochrome substituents in DAOTA series was also studied. The oxidative dimerization of cationic [4]helicene derivatives was also described. Two features were particularly emphasized: (i) the homochiral recognition in the intermolecular coupling and (ii) the kinetic and themodynamic atroposelectivity around the novel Csp2-Csp2 bond.