title: Heterochiral to Homochiral Transition in Pentahelicene 2D Crystallization Induced by Second-Layer Nucleation.
abstract: Gaining insight into molecular recognition at the molecular level, in particular, during nucleation of crystallites, is challenging and calls for studying well-defined model systems. Investigated by means of submolecular resolution scanning tunneling microscopy and theoretical molecular modeling, we report chiral recognition phenomena in the 2D crystallization of the helical chiral aromatic hydrocarbon pentahelicene on a Cu(111) surface. Homochiral, van der Waals bonded dimers constitute building blocks for self-assembly but form heterochiral as well as homochiral long-range-ordered structures. 2D racemate crystals, built up by homochiral dimers of both enantiomers, are observed at coverages close to a full monolayer. As soon as the coverage leads to second-layer nucleation, the dense racemate phase in the first layer disappears and a homochiral dimer conglomerate phase of lower 2D density appears. Our results show that, at the onset of second-layer nucleation, a local change of enantiomeric composition in the first layer occurs, causing the transition from a 2D racemate to a 2D conglomerate.
authors.affiliation: Nanoscale Materials Science, Empa, Swiss Federal Laboratories for Materials Science and Technology , Überlandstrasse 129, CH-8600 Dübendorf, Switzerland.
authors.forename: Anaïs
authors.initials: A
authors.lastname: Mairena
authors.affiliation: Department of Chemistry, University of Zurich , CH-8057 Zürich, Switzerland.
authors.forename: Laura
authors.initials: L
authors.lastname: Zoppi
authors.affiliation: Nanoscale Materials Science, Empa, Swiss Federal Laboratories for Materials Science and Technology , Überlandstrasse 129, CH-8600 Dübendorf, Switzerland.
authors.forename: Johannes
authors.initials: J
authors.lastname: Seibel
authors.affiliation: Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt , Max-von-Laue-Straße 7, 60438 Frankfurt, Germany.
authors.forename: Alix F
authors.initials: AF
authors.lastname: Tröster
authors.affiliation: Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt , Max-von-Laue-Straße 7, 60438 Frankfurt, Germany.
authors.forename: Konstantin
authors.initials: K
authors.lastname: Grenader
authors.affiliation: Nanoscale Materials Science, Empa, Swiss Federal Laboratories for Materials Science and Technology , Überlandstrasse 129, CH-8600 Dübendorf, Switzerland.
authors.forename: Manfred
authors.initials: M
authors.lastname: Parschau
authors.affiliation: Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt , Max-von-Laue-Straße 7, 60438 Frankfurt, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Terfort
authors.affiliation: Nanoscale Materials Science, Empa, Swiss Federal Laboratories for Materials Science and Technology , Überlandstrasse 129, CH-8600 Dübendorf, Switzerland.|Department of Chemistry, University of Zurich , CH-8057 Zürich, Switzerland.
authors.forename: Karl-Heinz
authors.identifier: 0000-0002-2077-4922
authors.initials: KH
authors.lastname: Ernst
keywords: 2D crystallization; chirality; helicenes; optical resolution; scanning tunneling microscopy