Synthesis, structure, linear and nonlinear properties of tricyanofuran–terminated merocyanine dyes

Abstract

Structural and spectroscopic characteristics of merocyanine dyes are important because of their potential applications in optoelectronics and sensors. Herein we report synthesis, X-ray diffraction characterization of crystal structure, spectroscopic and NMR studies of four merocyanine dyes which, according to their strong donor-acceptor structure, exhibit a second order polarizability (β). Crystallographic studies demonstrated an almost planar structure of all molecules and indicated the occurrence of conformational changes in π-conjugated bridge between donor and acceptor. For three homologues similar packing modes, defined mostly by week CH⋯N interactions, were found in crystals. Bond length alternation (BLA) values have been evaluated using crystallographic and NMR data and have shown a correlation to their nonlinear optical activity. Second order polarizabilities for all compounds were measured using hyper Rayleigh scattering (HRS) in solution. It was found that the merocyanines studied exhibit very large second order polarizabilities (up to 4.1 10−27 esu), making them potentially useful for materials for second harmonic generation (SHG). Unfortunately, they do not demonstrate acentric packing of chromophores, which is required for SHG in the crystalline state, but may show promise for other applications such as poled polymer blends or for SHG sensing in biological environments.