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Title: The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol

The assembly of complex structures in nature is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Understanding and ultimately controlling the self-assembly of materials requires extensive study of how these forces drive local nanoscale interactions and how larger structures evolve. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This paper focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol has recently been shown to have interesting properties as a chiral modifier of surface chemistry; however, its mode of action is not fully understood and a microscopic understanding of the role non-covalent interactions play in its adsorption and assembly on surfaces is lacking. In order to probe its surface properties, we employed high-resolution scanning tunneling microscopy and density functional theory (DFT) simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule’s intrinsic chiral center leading to monomers of like chirality, at both chiralmore » centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations, however, reveal that the tetramers are stable entities that are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. This network of homochiral square pores grows to cover the whole Au(111) surface. Our data reveal that the chirality of a simple alcohol can be transferred to its surface binding geometry, drive the directionality of hydrogen-bonded networks and ultimately extended structure. Finally and furthermore, this study provides the first microscopic insight into the surface properties of this important chiral modifier and provides a well-defined system for studying the network’s enantioselective interaction with other molecules.« less
Authors:
 [1] ;  [2] ;  [1] ; ORCiD logo [1] ;  [1] ;  [1] ;  [1] ;  [3] ;  [1]
  1. Tufts Univ., Medford, MA (United States). Dept. of Chemistry
  2. CIC energiGUNE, Miñano (Spain)
  3. Univ. College London (UCL) (United Kingdom). Thomas Young Centre. London Centre for Nanotechnology. Dept. of Physics and Astronomy
Publication Date:
Grant/Contract Number:
FG02-03ER15472; 616121; EP/F036884/1
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 9; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Tufts Univ., Medford, MA (United States); CIC energiGUNE, Miñano (Spain); Univ. College London (UCL) (United Kingdom)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); Ministry of Economy and Enterprise (MINECO) (Spain); European Research Council (ERC); Royal Society (United Kingdom); Engineering and Physical Sciences Research Council (EPSRC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chirality; isomerism; chemical bonding; chemical elements; scanning tunneling microscopy; intermolecular forces; gas phase; hydrogen bonding; density functional theory
OSTI Identifier:
1469315
Alternate Identifier(s):
OSTI ID: 1240033

Liriano, Melissa L., Carrasco, Javier, Lewis, Emily A., Murphy, Colin J., Lawton, Timothy J., Marcinkowski, Matthew D., Therrien, Andrew J., Michaelides, Angelos, and Sykes, E. Charles H.. The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol. United States: N. p., Web. doi:10.1063/1.4941560.
Liriano, Melissa L., Carrasco, Javier, Lewis, Emily A., Murphy, Colin J., Lawton, Timothy J., Marcinkowski, Matthew D., Therrien, Andrew J., Michaelides, Angelos, & Sykes, E. Charles H.. The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol. United States. doi:10.1063/1.4941560.
Liriano, Melissa L., Carrasco, Javier, Lewis, Emily A., Murphy, Colin J., Lawton, Timothy J., Marcinkowski, Matthew D., Therrien, Andrew J., Michaelides, Angelos, and Sykes, E. Charles H.. 2016. "The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol". United States. doi:10.1063/1.4941560. https://www.osti.gov/servlets/purl/1469315.
@article{osti_1469315,
title = {The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol},
author = {Liriano, Melissa L. and Carrasco, Javier and Lewis, Emily A. and Murphy, Colin J. and Lawton, Timothy J. and Marcinkowski, Matthew D. and Therrien, Andrew J. and Michaelides, Angelos and Sykes, E. Charles H.},
abstractNote = {The assembly of complex structures in nature is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Understanding and ultimately controlling the self-assembly of materials requires extensive study of how these forces drive local nanoscale interactions and how larger structures evolve. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This paper focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol has recently been shown to have interesting properties as a chiral modifier of surface chemistry; however, its mode of action is not fully understood and a microscopic understanding of the role non-covalent interactions play in its adsorption and assembly on surfaces is lacking. In order to probe its surface properties, we employed high-resolution scanning tunneling microscopy and density functional theory (DFT) simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule’s intrinsic chiral center leading to monomers of like chirality, at both chiral centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations, however, reveal that the tetramers are stable entities that are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. This network of homochiral square pores grows to cover the whole Au(111) surface. Our data reveal that the chirality of a simple alcohol can be transferred to its surface binding geometry, drive the directionality of hydrogen-bonded networks and ultimately extended structure. Finally and furthermore, this study provides the first microscopic insight into the surface properties of this important chiral modifier and provides a well-defined system for studying the network’s enantioselective interaction with other molecules.},
doi = {10.1063/1.4941560},
journal = {Journal of Chemical Physics},
number = 9,
volume = 144,
place = {United States},
year = {2016},
month = {3}
}