Self-assembling supramolecular columnar organogels formed by wedge shaped cesium 3,4,5-alkyloxy benzene sulfonates

Soft Matter, vol. 21, pp. 5055–5066

Abstract

A systematic investigation of the homologous series of cesium 3,4,5-tris(alkoxy) benzenesulfonates with different alkyl lengths was conducted to assess their capacity for low molecular weight organogels formation by self-assembling of fibrillar networks. Such goal was achieved through both spontaneous and quench gelation techniques at temperatures of +20 °C, -5 °C, and -20 °C across thirteen different organic solvents. The morphologies of representative gel samples, were monitored using electron microscopy. This analysis revealed the presence of cylindrical elementary fibrils approximately 5 nm in diameter, with sulfonate groups oriented to the axis of the cylinders. Furthermore, the formation of gel netpoints appears to be predominantly facilitated by local branching within fiber bundles. Wedge-shaped dendrons derived from benzenesulfonic acid exhibit a remarkable diversity of phase behavior, attributable to the potential for molecular shape modulation through incremental alterations in their chemical structure. Specifically, variations in the length of aliphatic tails, extending from 14 to 18 methylene units, induce significant transformations in phase behavior. At ambient temperature, these compounds manifest columnar ordered oblique phases in the bulk state. Upon heating they undergo transformation into columnar hexagonal disordered phases and to a cubic BCC phase. General gel structure-property relationships were established and discussed.

Authors 6

1. Uwe Beginn

   Osnabrück University

   Affiliation as printed

   Institute of Chemistry of New Materials, Barbabrastr. 7, University of Osnabrueck, 49076 Osnabrueck, Germany

2. A. A. Stupnikov

   Kurchatov Institute · Moscow State University of Fine Chemical Technologies

   Affiliation as printed

   National Research Center Kurchatov Institute, 1 pl. Akad. Kurchatova, 123182 Moscow, Russian Federation

   Russian Technological University, Institute of Fine Chemical Technologies, 86 Prosp. Vernadskogo, 119571 Moscow, Russian Federation

3. Artem V. Bakirov

   Kurchatov Institute · Russian Academy of Sciences · Institute of Synthetic Polymeric Materials

   Affiliation as printed

   Enikolopov Institute of Synthetic Polymeric Materials, Russian Academy of Science, 70 ul. Profsoyuznaya, 117393 Moscow, Russian Federation

   National Research Center Kurchatov Institute, 1 pl. Akad. Kurchatova, 123182 Moscow, Russian Federation

4. Maxim A. Shcherbina

   Russian Academy of Sciences · Institute of Synthetic Polymeric Materials · Centre of Advanced Studies

   Affiliation as printed

   Enikolopov Institute of Synthetic Polymeric Materials, Russian Academy of Science, 70 ul. Profsoyuznaya, 117393 Moscow, Russian Federation

   Moscow Center for Advanced Studies, 20 Kulakova Str., Moscow, Russian Federation

5. Martin Möller Aachen Institute of Technical and Macromolecular Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Technical and Macromolecular Chemistry, RWTH Aachen and DWI e.V., D 52056 Aachen, Germany

6. С. Н. Чвалун

   Kurchatov Institute · Russian Academy of Sciences · Institute of Synthetic Polymeric Materials

   Affiliation as printed

   Enikolopov Institute of Synthetic Polymeric Materials, Russian Academy of Science, 70 ul. Profsoyuznaya, 117393 Moscow, Russian Federation

   National Research Center Kurchatov Institute, 1 pl. Akad. Kurchatova, 123182 Moscow, Russian Federation