Ultra-efficient and stable electro-optic dendrimers containing supramolecular homodimers of semifluorinated dipolar aromatics†

Abstract

In organic electro-optic (EO) materials, strong dipole–dipole interactions hinder the highly efficient poling of nonlinear optical chromophores. Supramolecular self-assembly through p–p stacking of fluoroaromatics was proved to be one of the most effective strategies to simultaneously achieve high chromophore loading density and highly efficient poling. Herein, we demonstrated a new strategy of supramolecular homodimerization to self-assemble EO dendritic films, in which two dendritic units with semifluorinated dipolar 1,2,3-trifluorobenzene (TFB) moieties were attached to the donor end and the p-bridge centre of push–pull tetraene chromophores. In these new dendrimers, the use of monolithic and semifluorinated TFB rings to replace the heterodimers of phenyl and pentafluorophenyl moieties has greatly simplified the synthesis of dendrimers and their intermixing, and can further potentially enable more efficient and rapid intermixing of interacting moieties in the solid states than those in binary and ternary systems. Photophysical property analysis and DFT calculations were carried out to understand the macroscopic supramolecular self-assembly and microscopic polarizability of new TFB-based EO dendrimers. The poled films of these self-assembled dendritic EO films exhibited very large EO coefficients up to 248 pm V 1 at a wavelength of 1310 nm and excellent temporal stability at room temperature with a very minimal change of B5% for over 1000 hours. Our study therefore illustrates that homodimer stacking of TFB rings through dipole–dipole coupling provides stabilization energy similar to that of quadrupolar interaction of phenyl and pentafluorophenyl heterodimeric pairs. Due to the highly efficient poling and excellent temporal EO stability, TFB self-assembled EO dendrimers show great potential for application in photonic devices.