Macrocyclic Amphiphiles with 1,8-Anthrylene Fluorophores: Synthesis and Attempts toward Two-Dimensional Organization

Abstract

New macrocyclic amphiphiles with two or three integrated 1,8-anthrylenes have been synthesized by an iterative Sonogashira cross-coupling protocol. The final cyclization has been conducted with 80% yield under cuprous-free dilution conditions. Formation of a monolayer at the air/water interface has also been demonstrated. These results open the intriguing possibility to construct large 2D supramolecular/macromolecular systems for which unique photophysical and -chemical properties are expected.

Conjugated Macrocycles: Concepts and Applications

“…Macrocycle 103 with three C 3v -symmetrical 1,8-anthrylene units was designed as a monomer for the synthesis of 2D polymer 104 (Scheme 14). [83] Photochemical studies suggested that the macrocycle 103 had the potential to undergo UVinduced [4+4] cycloaddition at the anthracene unit without any undesired side reaction, thereby leading to the 2D polymer 104.…”

Synthesis of a Covalent Monolayer Sheet by Photochemical Anthracene Dimerization at the Air/Water Interface and its Mechanical Characterization by AFM Indentation

“…[ 33,34 ] In the course of the single-crystal approach to 2DPs, compounds 1 and 2 were synthesized which differ by the presence and absence, respectively, of a trimesic acid cap that combines the three hydroxyl groups of 2 . [ 22,[35][36][37] Compound 2 is amphiphilic and we reasoned that it may be a good candidate for an interfacial approach to synthesize a 2DP because of its orientation preference at the air/water interface, with the hydroxyl groups immersing into the aqueous phase and the hydrophobic part standing up into the air whereby the anthracenes would reside more or less at the same height above the interface. Ideally, either spontaneously or upon exertion of lateral pressure, the monomers could orient themselves such that the anthracene units of neighbouring monomers assume face-to-face (ftf) stacking.…”

Synthetische kovalente und nichtkovalente zweidimensionale Materialien

“…2014 wurde ein Monomer untersucht, [91] bei dem die Benzo-1,3,5-triat-Einheit der in Abbildung 5a gezeigten Struktur entfernt worden war, um eine Spezies mit drei Hydroxygruppen, die dem Molekül amphiphilen Charakter verleihen, zu erhalten (Abbildung 5c). [92] Dieses Monomer wurde für die 2D-Polymersynthese an der Luft/WasserGrenzfläche verwendet. [91] 3.…”