Engineering of Acentric Stilbazolium Salts with Large Second-Order Optical Nonlinearity and Enhanced Environmental Stability

Abstract

A series of organic nonlinear optical (NLO) materials based on the stilbazolium derivatives of 4-N,N-dimethylamino-4′-N′-methyl-stilbazolium tosylate (DAST) were synthesized, and the single crystals were grown from the solutions. Single-crystal structure determinations and Kurtz powder tests reveal that replacement of the p-toluenesulfonate anion in the DAST crystal, forming 4-N,N-dimethylamino-4′-N′-methyl-stilbazolium 4-aminotoluene-3-sulfonate (1) and 4-N,N-dimethylamino-4′-N′-methyl-stilbazolium p-chlorobenzenesulfonate (2), constructs new acentric crystals with quite a large powder second-harmonic generation (SHG) of more than 3 orders of magnitude larger than that of urea around 2.0 μm, whereas the other two complexes show their centrosymmetric structures without any SHG effects. A possible estimation of the molecular first hyperpolarizabilities βijk performed on 2 further confirms its origin of its enhanced NLO merits. Furthermore, both 1 and 2 exhibit even higher environmental stabilities, includi...