Chirality at two-dimensional surfaces: A perspective from small molecule alcohol assembly on Au(111)

Liriano, Melissa L.; Larson, Amanda M.; Gattinoni, Chiara; Carrasco, Javier; Baber, Ashleigh E.; Lewis, Emily A.; Murphy, Colin J.; Lawton, Timothy J.; Marcinkowski, Matthew D.; Therrien, Andrew J.; Michaelides, Angelos; Sykes, E. Charles H.

doi:10.1063/1.5035500

Cited by 11 publications

(12 citation statements)

References 53 publications

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“…The monoclinic crystalline structure can be readily obtained at a temperature close to melting or by annealing of the amorphous solid. Above a solid surface, ethanol molecules have been reported to form commensurate overlayer structures on gold and graphite (with high mosaic-angle disorder). , However, a detailed study of the structural and phase-transition evolution of ultrathin to multilayer ethanol films (transitioning from an interfacial structure to the bulk one) on highly ordered graphite is still lacking and thus needs further investigation.…”

Section: Introductionmentioning

confidence: 99%

Ethanol on Graphite: Ordered Structures and Delicate Balance of Interfacial and Intermolecular Forces

Yang

2021

J. Phys. Chem. C

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Clear knowledge of solid–molecule interfacial structures is essential to the understanding of interfacial phenomena and the interplay of surface effects and intermolecular forces. Molecules that can form hydrogen bonds are of particular interest. Here, we report the structures and phase-transition behavior of (sub)nanometer thick ethanol assemblies deposited on highly orientated pyrolytic graphite. Depending on the film thickness and temperature, three ordered structures of ethanol are observed: first, an interfacial one formed after deposition at ∼100 K that is near-commensurate with the supporting graphene lattice, up to a nominal thickness of 1.5 nm; second, stacking of two-dimensional layered sheets at ≥114 K for the upper part of thicker films of ∼2 nm and above; and third, a monoclinic bulk-like structure appearing at ∼144 K before desorption. Importantly, the whole amorphous-to-crystalline transition undergoes a complex multistep process, with the extension of the interfacial structure reaching much further away from the substrate surface and then being replaced within a low-temperature range. Together with the lattice strain found in the interfacial assembly, these thickness- and temperature-dependent structures and transition behavior signify a delicate balance between all interfacial and intermolecular forces involved and molecular free energy.

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Section: Introductionmentioning

confidence: 99%

Ethanol on Graphite: Ordered Structures and Delicate Balance of Interfacial and Intermolecular Forces

Yang

2021

J. Phys. Chem. C

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“…In the case of alcohol adsorption on bare metal surfaces, which has been reported previously, the two possible adsorption chiralities are energetically degenerate, although the interplay of hydrogen bonding can lead to both long-range homo and hetero chiral structures. [18][19][20][21][22]70 However, methanol on the "29" oxide is forced to adsorb into a particular chirality in order to satisfy the dual bonding motif, as shown in Figure 2C. While the adsorption chirality of methanol is not determined experimentally, the DFT model clearly shows that methanol has a favored adsorption chirality dictated by the geometry of the binding pocket based on the geometry of the dual hydrogen bonding and dative bonding adsorption motif.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Surface-Templated Assembly of Molecular Methanol on the Thin Film “29” Cu(111) Surface Oxide

et al. 2019

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Identifying and characterizing the atomic-scale interaction of methanol with oxidized Cu surfaces is of fundamental relevance to industrial reactions, such as methanol steam reforming and methanol synthesis. In this work, we examine the adsorption of methanol on the well-defined “29” Cu oxide surface, using a combination of experimental and theoretical techniques, and elucidate the atomic-scale interactions that lead to a unique spatial ordering of methanol on the oxide thin film. We determine that the methanol chain structures form first due to epitaxy with the underlying “29” oxide surface. Specifically, the geometry of the “29” oxide is such that there are spatially adjacent Oδ– sites, in the form of O adatoms, and Cuδ+ species, within the Cu2O-like rings, which allow for methanol to simultaneously bond to the surface via an Omethanol–Cuδ+ dative bond and an OHmethanol–Oδ– hydrogen bond. The methanol–oxide bond strength outweighs the strength of methanol–methanol hydrogen bonds on the “29” Cu oxide, unlike methanol assembly on bare coinage metal surfaces on which hydrogen bonding between adjacent molecules leads to ordered arrays. Weak, long-range interactions lead to the formation of chains of only even numbers of methanol molecules. Together, this work reveals that, unlike that on metal surfaces, the corrugation of the oxide surface drives methanol adsorption to preferred binding sites, preventing intermolecular hydrogen bonding and dictating the adsorption geometry.

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“…At a fundamental level, the delicate balance of intermolecular forces of varied strengths, noncovalent interfacial interactions between molecular overlayers and supporting substrate surfaces, molecular organizations and crystallographic symmetry, the existence of polymorphs, kinetic versus thermodynamic control, and/or spatial confinement constraint have a critical impact on the crystallization pathway and growth of molecular thin films as well as polymorph selectivity. − As a result of such complexity, it is often difficult to predict the structure of a molecular overlayer on a specific substrate, especially when the interfacial interaction is relatively weak and no significant guiding force such as chemisorption is directly involved. Rather unexpected results for physisorbed assemblies of small molecules have been discovered in recent years using structure-probing diffraction, − scanning probe, − and spectroscopic methods. , …”

Section: Introductionmentioning

confidence: 99%

Ordering of Small Molecules on Hydrophobic Self-Assembled n-Alkanethiols: Delicate Balance of Interfacial and Intermolecular Interactions

Ghosh

Yang

2021

J. Phys. Chem. C

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Growth of molecular thin films with desired orders and orientations has become technologically relevant as the electronic industries seek new opportunities and applications. However, the delicate balance of interfacial and intermolecular forces and their complex influence on thin-film growths still require more understanding. Here, the effects of a hydrophobic selfassembled monolayer (SAM) surface on the crystallization of four common solventsacetonitrile, ethanol, methanol, and waterare investigated. Despite the absence of significant substrate−molecule forces, unexpected oriented growth is observed for these molecules except water. Acetonitrile and ethanol form a sustaining vertical assembly order with long-range crystalline structures. Coincident epitaxy with small lattice mismatches is found to be essential to these orderings, which are energetically favored but without a dominant azimuthal orientation. In contrast, a preferred in-plane registry of methanol overlayers is observed for an ultrathin nominal thickness and becomes lost in slightly thicker films. Such thickness-dependent ordering of methanol assemblies can be explained with semi-commensurate epitaxy with a tensile strain of ∼6.6% along hydrogen-bonded chains, whose quick relief results in the loss of order and even the phase. These rich observations suggest that SAM surfaces offer good opportunities for selective crystallization of molecular films worthy of further investigations.

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Chirality at two-dimensional surfaces: A perspective from small molecule alcohol assembly on Au(111)

Cited by 11 publications

References 53 publications

Ethanol on Graphite: Ordered Structures and Delicate Balance of Interfacial and Intermolecular Forces

Ethanol on Graphite: Ordered Structures and Delicate Balance of Interfacial and Intermolecular Forces

Surface-Templated Assembly of Molecular Methanol on the Thin Film “29” Cu(111) Surface Oxide

Ordering of Small Molecules on Hydrophobic Self-Assembled n-Alkanethiols: Delicate Balance of Interfacial and Intermolecular Interactions

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