Solution Chemistry Effects on the Nonlinear Optical Properties of Phosphazenes

Abstract

Using the combination of experimental (DFWM) measurements and electronic structure calculations, ligand electron donating power and explicit solvent interactions were shown to have critical roles in enhancing the χ3 yields for phosphonitrilic materials. Experimental measurements have shown that decreasing solution pH to 1.0 can significantly increase the χ3 yield for P3N3(NHCH3)6 and P3N3(N(CH3)2)6. Corresponding electronic structure calculations indicate replacement of amino by thiomethyl groups will also significantly enhance these yields. Comparison of electrostatic-based solvation effects and explicit water molecules indicates that dielectric stabilization from the solvent plays a minor influence on χ3 in comparison to strategies which affect the strong P-N bond polarity.