The formation of single-layer-thick molecular networks at metal surfaces is governed by the interplay between intermolecular and interfacial interactions. This Review highlights how, with films built by vacuum deposition, these interactions can be modulated to form substrates that may be useful as catalysts or templates for further deposition steps.

Tailoring molecular layers at metal surfaces

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.

Enantiomer surface chemistry: conglomerate versus racemate formation on surfaces.

Initial stages of a chiral phase transition in the monolayer of a quinacridone derivative on the Au(111) surface were investigated by scanning tunneling microscopy at submolecular resolution. The prochiral molecules form a homochiral lamella phase at low coverages upon adsorption. A transition to a racemate lattice is observed with increasing coverage. Enantiomers of a homochiral lamella line become specifically substituted by opposite enantiomers such that a heterochiral structure evolves. Due to the higher density, lateral alkyl chains are bent away from the surface. Our findings are significant for the understanding and control of chiral phase transitions in related molecular systems like liquid crystals.

Direct Observation of Enantiospecific Substitution in a Two-Dimensional Chiral Phase Transition

Surface molecular self-assembly is a fast advancing field with broad applications in sensing, patterning, device assembly, and biochemical applications. A vast number of practical systems utilize alkane thiols supported on gold surfaces. Whereas a strong Au-S bond facilitates robust self-assembly, the interaction is so strong that the surface is reconstructed, leaving etch pits that render the monolayers susceptible to degradation. By using different head group elements to adcust the molecule-surface interaction, a vast array of new systems with novel properties may be formed. In this paper we use a carefully chosen set of molecules to make a direct comparison of the self-assembly of thioether, selenoether, and phosphine species on Au(111). Using the herringbone reconstruction of gold as a sensitive readout of molecule-surface interaction strength, we correlate head-group chemistry with monolayer (ML) properties. It is demonstrated that the hard/soft rules of inorganic chemistry can be used to rationalize the observed trend of molecular interaction strengths with the soft gold surface, that is, P>Se>S. We find that the structure of the monolayers can be explained by the geometry of the molecules in terms of dipolar, quadrupolar, or van der Waals interactions between neighboring species driving the assembly of distinct ordered arrays. As this study directly compares one element with another in simple systems, it may serve as a guide for the design of self-assembled monolayers with novel structures and properties.

Effect of head-group chemistry on surface-mediated molecular self-assembly.

A combination of theory and experiment is used to interrogate the surface bonding geometry and rotational dynamics of a simple asymmetric thioether, butyl methyl sulfide. Calculations predict that binding occurs to a Au surface through one of the lone pairs on the sulfur atom and that the alkyl tails lie almost parallel to the surface. The unbonded lone pair remains unperturbed, and the geometry around the S atom is essentially tetrahedral, and hence two surface-bound enantiomers of the prochiral molecule are formed with an R-S inversion barrier that is predicted to be large. The rapidly rotating molecules can be clearly distinguished upon atomic-scale imaging by their mirror image pinwheel appearance. The binding of asymmetric dialkyl sulfides leads to the formation of surface-bound enantiomers, which has important consequences for studies in which thioether linkers are used in conjunction with chiral moieties and indicates that diastereomeric effects may be at play in these systems.

Chirality and Rotation of Asymmetric Surface-Bound Thioethers†

We present a low-temperature scanning tunneling microscopy study of increasing coverages of 2,5-dichlorothiophenol, an asymmetrically halo-substituted aromatic thiol, on Cu(111). At low coverage, deprotonation of the thiol occurs spontaneously upon adsorption at 80 K. Albeit the low deposition temperature, we find the formation of adsorbate islands at low coverage, which coalesce into a well-ordered film of horizontally adsorbed molecules at increasing coverage. This behavior indicates (i) significant mobility of the thiols on Cu(111) even at low temperatures and (ii) attractive adsorbate-adsorbate interactions. At higher coverages intermolecular interactions prevent long-range diffusion of adsorbates and thermal activation of the S-H bond becomes necessary. A close analysis of the molecular films reveals chiral recognition between neighboring molecules, which leads to the formation of enantiopure areas on the surface. Upright orientation of individual molecules starts at the boundaries between such phases and can be induced by scanning tunneling microscopy.

http://research.chem.ucr.edu/groups/bartels//publications/langmuir20p4406.pdf

J. Zhang

Papers

Low-temperature mobility and structure formation of a prochiral aromatic thiol (2,5-dichlorothiophenol) on Cu(111).