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.

SummaryChromophore-functionalized, chiral, helical polybinaphthalenes with acetylene linkage have been prepared by functionalization of precursor polymers. The chromophores seem to be chirally ordered in these materials. This property, and the large possibilities for architectural diversification, make these materials promising candidates for nonlinear optical studies as well as applications thereof.

Summary: In this paper two new donor‐embedded polybinaphthalenes prepared by the Heck reaction are presented. By introducing a double bond in the polymer backbone, the supramolecular structure was altered in comparison with polymers without the double bond. Comparison between the CD/UV‐Vis spectra of polymers, with and without the double bond (previously synthesized in our laboratory) proved this change in a supramolecular structure. The double bonds also allow crosslinking upon heat treatment. NLO experiments demonstrated a more stable nonlinearity over time depending on the degree of crosslinking. magnified image

New, pyranone-based chromophores were synthesized and their (nonlinear) optical properties were measured. The chromophores were prepared by first condensing an electron withdrawing group with pyranone, followed by reaction with an aldehyde-functionalized πconjugated bridged donor molecule. This approach enables one to easily incorporate the pyranone moiety and to prepare both linear and Λ-shaped chromophores. The (nonlinear) optical properties were measured using femtosecond hyper-Rayleigh scattering. These measurements demonstrated the advantages of this approach.