title: Pathway Complexity in the Enantioselective Self-Assembly of Functional Carbonyl-Bridged Triarylamine Trisamides.
abstract: Functional supramolecular systems like carbonyl-bridged triarylamine (CBT) trisamides are known for their long-range energy transport at room temperature. Understanding the complex self-assembly processes of this system allows for control over generated structures using controlled supramolecular polymerization. Here, we present two novel CBT trisamides with (S)- or (R)-chiral side chains which show a two-pathway self-assembly behavior in solution. Depending on the thermal profile during the self-assembly process, two different stable states are obtained under otherwise identical conditions. A kinetically trapped state A is reached upon cooling to 7 °C, via a proposed isodesmic process. In addition, there is a thermodynamically stable state B at 7 °C that is induced by first undercooling to -5 °C, via a nucleation-elongation mechanism. In both cases, helical supramolecular aggregates comprising H-aggregated CBTs are formed. Additionally, controlled supramolecular polymerization was achieved by mixing the two different states (A and B) from the same enantiomer, leading to a conversion of the kinetically trapped state to the thermodynamically stable state. This process is highly enantioselective, as no conversion is observed if the two states consist of opposite enantiomers. We thus show the importance and opportunities emerging from understanding the pathway complexity of functional supramolecular systems.
authors.affiliation: Department of Chemical Engineering and Chemistry, Institute for Complex Molecular Systems and Laboratory of Molecular Science and Technology, Eindhoven University of Technology , P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
authors.forename: Andreas T
authors.initials: AT
authors.lastname: Haedler
authors.affiliation: Department of Chemical Engineering and Chemistry, Institute for Complex Molecular Systems and Laboratory of Molecular Science and Technology, Eindhoven University of Technology , P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
authors.forename: Stefan C J
authors.initials: SC
authors.lastname: Meskers
authors.affiliation: Department of Chemical Engineering and Chemistry, Institute for Complex Molecular Systems and Laboratory of Molecular Science and Technology, Eindhoven University of Technology , P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
authors.forename: R Helen
authors.initials: RH
authors.lastname: Zha
authors.affiliation: Chair of Organic Chemistry I, Department of Chemistry and Pharmacy, Friedrich-Alexander University Erlangen-Nürnberg , 91054 Erlangen, Germany.
authors.forename: Milan
authors.initials: M
authors.lastname: Kivala
authors.affiliation: Macromolecular Chemistry I, Bayreuth Institute of Macromolecular Research, and Bayreuth Center for Colloids and Interfaces, University of Bayreuth , 95440 Bayreuth, Germany.
authors.forename: Hans-Werner
authors.initials: HW
authors.lastname: Schmidt
authors.affiliation: Department of Chemical Engineering and Chemistry, Institute for Complex Molecular Systems and Laboratory of Molecular Science and Technology, Eindhoven University of Technology , P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
authors.forename: E W
authors.initials: EW
authors.lastname: Meijer