Polysilanes with NLO chromophores as pendant groups by utilizing different synthetic strategies

This paper summarizes our research on the synthesis and properties of several kinds of functionalized polysilanes (FPSs) containing nonlinear optic (NLO) chromophores in the side chain. They have been synthesized successfully through utilizing different synthetic strategies: chloromethylation of poly(methylphenylsilanes) and the following etherification with the hydroxy-containing NLO chromophore in water–chloroform two-phase system with Brij35 as a phase-transfer catalyst; hydrosilylation of polyhydrosilanes with the NLO chromophore containing the terminal double bond; etherification of chlorine-containing polysilanes with the hydroxy-containing NLO chromophore; and post-functionalization of phenyl group-containing polysilanes through azo coupling with p-nitrobenzenediazonium fluoroborate or tricyanovinylation with the oxidant tetracyanoethylene. FPSs were characterized with FT-IR, UV–vis spectra, differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and elemental analysis. The second-order optical nonlinear properties of the polysilanes were determined by in situ second harmonic generation (SHG) experiments.