Versatile Synthesis of Small NLO-Active Molecules Forming Amorphous Materials with Spontaneous Second-Order NLO Response

A novel synthetic approach to a series of bulky triarylamines substituted by various electron-withdrawing groups and forming amorphous materials is presented. Under vacuum evaporation, thin films with high optical quality are obtained and exhibit spontaneous second-order nonlinear optical activity. This unprecedented result is likely due to subtle balance between strong dipole-dipole interactions and steric crowding causing self-assembly and noncentrosymmetric local ordering, stable up to one year.