Enantiomer surface chemistry: conglomerateversusracemate formation on surfaces
- 1 January 2017
- journal article
- review article
- Published by Royal Society of Chemistry (RSC) in Chemical Society Reviews
- Vol. 46 (24), 7787-7839
- https://doi.org/10.1039/c7cs00555e
Abstract
Research on surface chirality is motivated by the need to develop functional chiral surfaces for enantiospecific applications. While molecular chirality in 3D has been the subject of study for almost two centuries, many aspects of 2D chiral surface chemistry have yet to be addressed. In 3D, racemic mixtures of chiral molecules tend to aggregate into racemate (molecularly heterochiral) crystals much more frequently than conglomerate (molecularly homochiral) crystals. Whether chiral adsorbates on surfaces preferentially aggregate into heterochiral rather than homochiral domains (2D crystals or clusters) is not known. In this review, we have made the first attempt to answer the following question based on available data: in 2D racemic mixtures adsorbed on surfaces, is there a clear preference for homochiral or heterochiral aggregation? The current hypothesis is that homochiral packing is preferred on surfaces; in contrast to 3D where heterochiral packing is more common. In this review, we present a simple hierarchical scheme to categorize the chirality of adsorbate-surface systems. We then review the body of work using scanning tunneling microscopy predominantly to study aggregation of racemic adsorbates. Our analysis of the existing literature suggests that there is no clear evidence of any preference for either homochiral or heterochiral aggregation at the molecular level by chiral and prochiral adsorbates on surfaces.Keywords
Funding Information
- U.S. Department of Energy (DE-SC0008703)
This publication has 340 references indexed in Scilit:
- Molecular chirality at surfacesPhysica Status Solidi (b), 2012
- Chiral Pinwheel Clusters Lacking Local Point ChiralitySmall, 2012
- Organization of the enantiomeric and racemic forms of an amphiphilic resorcinol derivative at the air–water and graphite–1‐phenyloctane interfacesChirality, 2011
- Attempts to explain the self-disproportionation observed in the partial sublimation of enantiomerically enriched carboxylic acidsJournal of Fluorine Chemistry, 2010
- Solvent effects on two-dimensional molecular self-assemblies investigated by using scanning tunneling microscopyCurrent Opinion in Colloid & Interface Science, 2008
- Tracking the Chiral Recognition of Adsorbed Dipeptides at the Single‐Molecule LevelAngewandte Chemie-International Edition, 2007
- Guanine Quartet Networks Stabilized by Cooperative Hydrogen BondsAngewandte Chemie-International Edition, 2005
- Expression of Chirality by Achiral Coadsorbed Molecules in Chiral Monolayers Observed by STMAngewandte Chemie-International Edition, 1998
- The origin and amplification of biomolecular chiralityOrigins of life and evolution of the biosphere, 1991
- Zur Kenntniss der Terpene und der ätherischen Oele. Ueber gebromte Derivate der CarvonreiheEuropean Journal of Organic Chemistry, 1895