Effects of Counterions with Multiple Charges on the Linear and Nonlinear Optical Properties of Polymethine Salts

Abstract

Counterions with multiple charges have been used to organize polymethines into multichromophore salt complexes. The intramolecular Coulombic interactions between multiply charged counterions and polymethines can play a significant role in modifying intermolecular interactions (i.e., aggregation). Here, we report a detailed study of the linear and nonlinear optical properties of such complexes with dications and hexacations over a large range of molecular concentrations. Our results have demonstrated that, despite strong intramolecular interactions, the preorganization of chromophores into the multichromophore salt constructs with multiple charges can provide a steric repulsive effect that can mitigate intermolecular interactions in the solid state. This results in a more efficient translation between microscopic and macroscopic optical properties for highly polarizable polymethines, which is essential for all optical signal switching.