Two-dimensionally conjugated molecules: The importance of low molecular symmetry for large third-order nonlinear optical effects

Low molecular symmetry with regard to the conjugation path of the delocalized electrons was found to be a good guideline towards linearly conjugated molecules with large second-order hyperpolarizabilities γ. We show that this guideline is also valid for two-dimensionally conjugated systems. We experimentally demonstrate this by third-harmonic generation measurements of two-dimensionally conjugated organic molecules, and show that the observed effects can be explained by the symmetry of the electronic wave functions. In addition, the positive impact of the substitution of phenyl rings by thienyl rings on γ is discussed.