8 new chiral, chromophore-functionalized donor-embedded polybinaphthalenes were prepared and characterized for their (nonlinear) optical properties. The polymers were prepared by direct polymerization using a Stille coupling reaction between a chiral bis(trimethyltin) binaphthalene derivative and diiodo-functionalized chromophores. The use of diiodo-functionalized instead of dibromo-functionalized chromophores resulted in a significant increase of molecular weight, as demonstrated by end-group analysis, GPC and MALDI-TOF experiments. The reaction conditions allowed the use of a great variety of chromophores with different DπA-structures. The typical treelike macromolecular architecture of the polymers is reflected in the behavior of the glass transition temperature and, more clearly, in the nonlinear optical properties. The nonlinear optical response shows a continuous, linear increase in function of chromophore concentration, indicating that the dipolar interactions between the chromophores are eliminated. Moreover, chiral contributions to the nonlinear optical response were observed and mounted 14 % of the highest achiral contribution.

Abstract. A series of chiral, chromophore-functionalized donor-embedded polybinaphthalenes were prepared by a Stille coupling reaction between a diiodo-functionalized chromophore and a 2 bis(trimethyltin) binaphthalene derivative. The optical purity of the chiral binaphthalene monomer was varied and its influence on the conformation of the polymers was investigated. Differential scanning calorimetry (DSC) and second-harmonic generation (SHG) experiments revealed that the mobility of the chromophore in the polymers, prepared from optically impure monomers, is much higher than in that of polymers obtained by polymerization of optically pure monomers. Hyper-Rayleigh scattering (HRS) measurements demonstrated that this difference in mobility is due to a different macromolecular structure.

A series of chromophore-functionalized polybinaphthalenes have been prepared and characterized for their (nonlinear optical) properties. The polymers were prepared by direct polymerization using a Stille coupling between a bis(trimethyltin) compound and dibromo-substituted binaphthalene monomers. The chromophores were attached to the binaphthalene unit via an alkyl spacer. The influence of the chromophore concentration, spacer length, and number of chromophores per binaphthalene unit was studied. The typical treelike macromolecular architecture of these molecules gives rise to a unique behavior in the glass transition temperature, NMR, and nonlinear optical properties. The nonlinear optical response shows a continuous increase in function of the chromophore content. In this way, the nonlinear optical properties can be increased in a way that is not possible with other chromophore-functionalized polymer materials.

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Nonlinear optical vinyl polymers with high glass transition temperature (Tg) were prepared by the functionalization of a fluorinated acrylate‐methyl vinyl isocyanate copolymer. A modified pathway to obtain a thiophene bridged chromophore was worked out. Poled films of the polymers show a fairly high and stable nonlinear optical response, even at elevated temperatures.