(Dicyanomethylene)pyran derivatives with C-2v symmetry: An unusual class of nonlinear optical chromophores

A series of symmetric derivatives of 4-(dicyanomethylene)-2-methyl-6-(p-(dimethylamino)styryl)-4H-pyran (DCM laser dye) has been synthesized, and the nonlinear optical properties and thermal decomposition temperatures of each of the chromophores has been measured. The symmetric chromophores all have larger hyperpolarizabilities than one would expect based on their absorption maxima. Estimations of their oscillator strengths based upon UV/vis spectra are all well above 1.0. It is proposed that these compounds possess two excited electronic states close to each other in energy, both contributing to the hyperpolarizability in an additive fashion. Electro-optical absorption spectroscopy data and semiempirical calculations on a model compound support this hypothesis. The implications of these results with regarded to the tradeoff between nonlinearity and transparency are discussed. The large dipole moments and high decomposition temperatures of these chromophores make them attractive candidates for use in electro-optic polymers.