Family of bis-Acridinium Receptors: Supramolecular Self-

Assemblies, Multi-Switching and Transport Properties

Henri-Pierre Jacquot de Rouville
Institut de Chimie de Strasbourg, CNRS/UMR 7177, 4 rue Blaise Pascal, 67000 Strasbourg, France.

In Nature, the high degree of organization allows the formation of sophisticated assemblies (double helical structure of DNA, G-quadruplex secondary structures, etc.) able to perform advanced functions (modulation of reactivity, movement, etc.). In such complex mixtures, the organization is governed by selective molecular recognition and self-assembly processes1 relying on weak interactions (hydrophobic, hydrogen-bonding, van der Waals, and pi-pi stacking interactions). Consequently, a growing interest in elaborating self-assembling systems has emerged in order to prepare functional synthetic systems in a simple and reliable manner.

We recently reported bis-acridinium receptors able to bind guest molecules.2 Based on molecular tweezers and their cyclophane analogues, two acridinium recognition units linked by a semi-rigid spacer are pre-organized to bind a variety of aromatic guests. The acridinium recognition units are unique multi-responsive building blocks (electrochemically and chemically switchable) able to interact with electron rich guests.3 Surprisingly, this class of bis- acridinium receptors exhibit i) self-complementary behaviors leading to the formation of entwined dimers,2a ii) narcissistic self-sorting as well2b as iii) pi-donor/pi-acceptor host-guest behaviors.4 In addition, the multi-switching properties of these bis-acridinium receptors were investigated to alter the recognition events and were also studied as selective phase transfer agents of perylene in perfluorocarbons.

Figure 1. Self-Assembly Processes and Switching Properties of a bis-acridinium Cyclophane.

References:

1. a) D. J. Cram, J. M. Cram, Science, 1974, 183, 803–809. b) J.-M. Lehn, Science, 1985, 227, 849–856. c) J.-M. Lehn, Angew. Chem., Int. Ed. Engl., 1990, 29, 1304–1319. d) J.-M. Lehn, Supramolecular Chemistry: Concepts and Perspectives; Wiley-VCH: New York, NY, 1995. e) J. Rebek, Chem. Soc. Rev., 1996, 25, 255–264. 2. a) H.-P. Jacquot de Rouville, N. Zorn, E. Leize-Wagner, V. Heitz, Chem. Commun., 2018, 54, 10966–10969; b) H.-P. Jacquot de Rouville, C. Gourlaouen and V. Heitz, Dalton Trans., 2019, 48, 8725–8730. 3 H.-P. Jacquot de Rouville, J. Hu, V. Heitz, ChemPlusChem, 2021, 86, 110–129.J. Hu, J. S. Ward, A. Chaumont, K. Rissanen, J.-M. Vincent, V. Heitz, H.- P. Jacquot de Rouville, Angew. Chem. Int. Ed., 2020, 59, 23206–23212.