Heck and Sonogashira cross-coupling reactions have been used for the functionalization of the upper rim of a tetraiodinated calix [4] arene. In this way, oligophenylenevinylene (OPV) and oligophenyleneethynylene (OPE) arrays have been constructed on the calix [4] arene core to produce covalent assemblies of four π-conjugated chromophores. Electrochemical properties have been investigated by cyclic voltammetry in different solvent/electrolyte ...