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Ionic Liquid Crystals Confined in Nanoporous Solids: Self-Assembly, Molecular Mobility and Electro-Optical Functionalities

Subject Area Physical Chemistry of Solids and Surfaces, Material Characterisation
Experimental Condensed Matter Physics
Term from 2019 to 2024
Project identifier Deutsche Forschungsgemeinschaft (DFG) - Project number 430146019
 
Final Report Year 2025

Final Report Abstract

The aim of the project was to explore the phase behaviour of ionic liquid crystals (ILCs) embedded in nanoporous solids and to relate it to the corresponding bulk phenomenology. By tailored synthesis wedge-shaped and rod-shaped ILCs based on benzoates and amino acids with guanidinium ion or crown ether cation complexes as ionic headgroups were obtained. These ILCs were confined in monolithic nanoporous aluminum oxide (AAO) membranes, with pore sizes of 25 - 180 nm and their mesomorphic properties, orientation, and molecular dynamics in nanoconfinement were investigated. A rich mesomorphic behaviour in nanoconfinement deviating from the bulk properties was observed. Synchrotron-based X-ray diffraction, dielectric spectroscopy, and calorimetry provided detailed insights into the structure and molecular dynamics of the confined mesogens. In addition, functionalities, such as optical anisotropy, optical activity and electrical conductivity were examined by linear birefringence, circular birefringence and dielectric spectroscopy, respectively. The results revealed that the molecular structure of the ILCs controlled the structure of the mesophase, whereas the choice of pore surface chemistry (i.e. hydrophilic or hydrophobic pore walls) and pore size played an important role on the surface alignment and configuration of the mesophase (i.e. axial, radial, log-pile, circular concentric) in the confinement of monolithic pores. NCILC is a multidisciplinary project involving 3 research teams, which profits from the complementary expertise, i.e. tailored synthesis of ILCs (Laschat), microscopic translational and orientational order (Huber), thermodynamics and molecular dynamics (Schönhals). 6 joint peer-reviewed papers were published by NCILC in journals with high impact factor like ACS Nano. Further publications are in progress. The results of NCILC sparked new scientific questions with new materials, leading to a new joint proposal with new innovative aims, which will be submitted soon.

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