Calix[4]arenes as molecules for second order nonlinear optics

The synthesis of a novel class of molecules for second order nonlinear optics, i.e. calix[4]arenes with extended π-systems, is described. These compounds are obtained via Wittig-Horner reactions of the formylated calix[4]arenes 5 and 6 to give the stilbene derivatives 7–9, or by diazotization of calix[4]arene, 1, followed by alkylation to give the phenylazocalix[4]arenes 11 and 12. The molecular second order nonlinear optical properties (βz) of these calix[4]arenes have been measured by electric field-induced second harmonic generation. The influence of different acceptors as well as the influence of the different conformations of the calix[4]arenes on βz values were determined. Surprisingly, the wavelength of the charge-transfer band λmax is lower when βz increases upon increasing the number of acceptors.