Nonlinear optical properties of molecular twins

Abstract

Three different series of twin nonlinear optic (NLO) molecules were studied, in which the two NLO chromophores are linked by a central flexible polymethylene spacer. The first series, which had two azobenzene chromophores (Azo-twins), was designed to also exhibit liquid crystallinity. Most of the members of this series exhibited a nematic mesophase. The second series had two 4-nitrophenol units as chromphores (PNP-twins), while the third one was based on 4-alkylsulfonyl-4'-alkoxy azobenzene chromophores (Sulfazo-twins). These twin NLO systems exhibited interesting odd-even oscillations in their second harmonic generation (SHG) efficiencies in the powder form. When the spacer had an odd number of methylene groups, they exhibited significantly higher powder SHG efficiency than their even counterparts, with the even ones most often exhibiting no detectable SH signal. Preliminary single crystal X-ray diffraction studies performed on the PNP-twin series showed that while the even members possess a molecular center of symmetry and pack centro-symmetrically, the odd ones do not, leading to the observed alternation. The orientational-disordering dynamics of two of the twin series - the PNP and the Sulfazo-twin series, doped in a poly(methyl methacrylate) matrix, was also studied by monitoring the SH-signal decay in electric field poled samples. Interestingly, the maximum attainable SH signal, χ⁽²⁾, in the poled samples also showed an odd-even oscillation with the odd ones again exhibiting a higher value of χ⁽²⁾. The temporal stability of the SHG intensity at 70°C, after the removal of the applied corona, was also studied and the relaxation of the chromophores was found to follow a biexponential decay. The slower relaxation component exhibits a spacer length dependence, which suggests the interplay of two factors in governing the temporal stability in such polymer doped twin systems, one is the conformational discomfort experienced by the spacer in adopting a U-shaped geometry, and the other the electrostatic repulsion when two aligned dipoles lie very close to each other.