Synthesis and second-order nonlinear optical properties of push-pull BODIPY derivatives

A series of boron dipyrromethene derivatives bearing an electron-donating 4-(dimethylamino)phenylethynyl group and an electron-withdrawing 4-nitrophenylethynyl group in the opposite 2- and 6-positions have been synthesized by Knoevenagel condensation followed by sequential Sonogashira coupling reactions. The compounds have been fully characterized with various spectroscopic methods. Their electrochemical properties have also been studied by cyclic voltammetry in CH2Cl2. It has been found that expansion of the pi systems by introduction of the 4-dodecyloxystyryl or 4-(dimethylamino) phenylethynyl group results in lowering of the first oxidation potential, while the first reduction potential remains relatively unaffected. The second-order nonlinear optical properties of these compounds have also been studied by electric-field-induced second-harmonic generation method in CHCl3. The values of the dot product mu.beta are in the range from 94x10(-48) to 330x10(-48) esu at 1907 nm, depending the substituents at the 3- and 5-positions. (C) 2012 Elsevier Ltd. All rights reserved.