Influence of Monomer Optical Purity on the Conformation and Properties of Chiral, Donor-Embedded Polybinaphthalenes for Nonlinear Optical Purposes

Abstract

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.

Tuning Soft Nanostructures in Self‐assembled Supramolecular Gels: From Morphology Control to Morphology‐Dependent Functions

“…[ 82 ] Of particular interest is the investigation of the role of chiral ordering towards the effi ciency of macroscopic devices. [ 83 ] Recently, chiral structures have been extended to chiral nanomaterials with plasmonic chirality and their application as metamaterials have been extensively investigated. [ 84,85 ] Supramolecular gelation provided an effective way to fabricate uniform chiral structures in large quantities, thus, supramolecular gels with chiral architectures might provide more chances to fabricate these advanced materials.…”

Polybinaphthyls incorporating chiral 2,2′-binaphthyl and isoquinoline moieties by Sonogashira reaction

“…The dihedral angle between two naphthalene rings of a binaphthyl molecule ranges from 60 to 120 , which leads to the kinked or twisted polymer main chain backbone [9,33e 35]. According to Samyn's report [33,36], the chiral polymer incorporating chiral R or S binaphthyl units into the main chain of polymer backbone can adopt a helical configuration. But no helical configuration can be formed if racemic 1,1 0 -binaphthyl monomers are incorporated into the same polymer backbone, it may form a random-coil-like structure.…”

Synthesis of Binaphthyl-Based Push-Pull Chromophores with Supramolecularly Polarizable Acceptor Ends

“…On the other hand, molecular chirality offers simple design principles for push-pull and noncentrosymmetric molecules, and the nanostructuring via self-assembly of chiral organic dyes has been shown to have pronounced effects and amplifications of their SHG response [9]. Binaphthyl compounds have been exploited for the realization of second-order nonlinear optical (NLO) materials, having the combined advantages of being chromophores and carrying the required element of chirality for bulk anisotropy [10][11][12][13][14][15][16][17]. In fact, binaphthyl systems, such as that shown in Figure 1, are composed of two chromophores joined through an aryl-aryl bond, which is the element (axis) of chirality, with dihedral angles usually close to 90 ∘ , so that interchromophoric conjugation is not efficient.…”

“…The application of the binaphthyl compounds in the field of nanosciences is recent and not yet fully explored [18][19][20][21][22][23][24][25][26][27][28][29]. In all previously reported examples of binaphthyl dyes for NLO applications, the molecular design expressing the push-pull concept was developed by placing electron donating groups in the 2,2 positions and the electron accepting units in the 6,6 positions ( Figure 1) [10][11][12][13][14][15][16][17].…”