Ionically self-assembled monolayer (ISAM) films have been recently shown to spontaneously produce noncentrosymmetric ordering that gives rise to a substantial second order nonlinear optical (NLO) response. Typically, the ISAM films for NLO response are an assemblage of bilayers of oppositely charged polymers whose thickness can be controlled through variation of pH and ionic strength of the immersion solutions. Here, we study the effects of replacing the NLO-active polymer layers with layers of dianionic molecules. Films fabricated exclusively using polyelectrolytes contain some fraction of both randomly oriented and anti-parallel oriented chromophores. The incorporation of dianionic molecules within the ISAM films affords greater χ(2) due to increased net polar orientation of the chromophores.