title: Chiral switching by spontaneous conformational change in adsorbed organic molecules.
abstract: Self-assembly of adsorbed organic molecules is a promising route towards functional surface nano-architectures, and our understanding of associated dynamic processes has been significantly advanced by several scanning tunnelling microscopy (STM) investigations. Intramolecular degrees of freedom are widely accepted to influence ordering of complex adsorbates, but although molecular conformation has been identified and even manipulated by STM, the detailed dynamics of spontaneous conformational change in adsorbed molecules has hitherto not been addressed. Molecular surface structures often show important stereochemical effects as, aside from truly chiral molecules, a large class of so-called prochiral molecules become chiral once confined on a surface with an associated loss of symmetry. Here, we investigate a model system in which adsorbed molecules surprisingly switch between enantiomeric forms as they undergo thermally induced conformational changes. The associated kinetic parameters are quantified from time-resolved STM data whereas mechanistic insight is obtained from theoretical modelling. The chiral switching is demonstrated to enable an efficient channel towards formation of extended homochiral surface domains. Our results imply that appropriate prochiral molecules may be induced (for example, by seeding) to assume only one enantiomeric form in surface assemblies, which is of relevance for chiral amplification and asymmetric heterogenous catalysis.
authors.affiliation: Interdisciplinary Nanoscience Center at the University of Aarhus (iNANO), Department of Physics and Astronomy, University of Aarhus, DK-8000 Aarhus C, Denmark.
authors.forename: Sigrid
authors.initials: S
authors.lastname: Weigelt
authors.forename: Carsten
authors.initials: C
authors.lastname: Busse
authors.forename: Lars
authors.initials: L
authors.lastname: Petersen
authors.forename: Eva
authors.initials: E
authors.lastname: Rauls
authors.forename: Bjørk
authors.initials: B
authors.lastname: Hammer
authors.forename: Kurt V
authors.initials: KV
authors.lastname: Gothelf
authors.forename: Flemming
authors.initials: F
authors.lastname: Besenbacher
authors.forename: Trolle R
authors.initials: TR
authors.lastname: Linderoth