Luminescence modulation in liquid crystalline phases containing a dispiro[fluorene-9,11′-indeno[1,2-b]fluorene-12′,9′′-fluorene] core

Abstract

A luminescent liquid crystalline compound containing a bulky dispiro[fluorene-9,11′-indeno[1,2-b]fluorene-12′,9′′-fluorene] has been designed and synthesized by di-substitution of a bromo derivative with N-(4-ethynylphenyl)-3,4,5-tris(hexadecyloxy)benzamide fragments. This di-substituted 3π–2spiro derivative forms stable and well-organized mesophases over large temperature ranges. Combination of DSC, POM and SAXS analyses has revealed the formation of a lamellar mesophase between 60 and 150 °C followed by another mesophase with a 2-dimensional lattice of rectangular symmetry that remains up to the isotropization point near 225 °C. In the original molecular packing model deduced from SAXS, the tert-butyl terminal groups fill the centre of hollow columns constituted by both the dihydro(1,2-b)indenofluorene and benzamide fragments and separated from each other by the surrounding aliphatic tails. The merging of the columns yielding the lamellar phase turned out to be governed by the dynamics of both, the micro-phase segregation process and the network of hydrogen bonds. In the various mesomorphic states and in solution, a strong luminescence was observed. The emission spectrum however depends on temperature and drastically changes between both mesophases and the isotropic liquid. In particular, a strong modulation of the emission wavelength occurs at the isotropic to 2D phase transition. This luminescence modulation results from an enhanced contribution of the vibronic peaks at higher energies in the emission profile. The compound was also found to be soluble in 5CB and was integrated in a guest–host LC cell, allowing efficient modulation of the photoluminescence polarization, in the presence or absence of an electrical field.