Non-covalent interactions: Halogen bonded 2D layers

Researchers: Prof Stuart Clarke

We have a longstanding and on-going interest in 2D monolayer of molecular materials and their structures. We have investigated a range of intermolecular interactions between the adsorbed molecules from van der Waals interactions, to dipolar species (refs. 1-4). This goes from ubiquitious van der Waals interactions (refs. 5-6) and supramolecular, non-covalent bonding interactions such as hydrogen bonding (refs. acids 7-10, amides 11-14, alcohols 15-17) and more recently halogen bonding (refs. 18-21).

Some images below illustrate some of the binary mixture 2D layers held together by halogen bonding. Halogen bonding is an interesting and relatively new interaction very similar is some ways to hydrogen bonding. It is reasonably strong and directional, by is not a permanent covalent bond. As illustrated in the table below, by changing the chemical nature of the components, strong and weak halogen bonds can be found. In the limit of very weak halogen bonds, no co-crystal forms at all.

A table of organic compounds and their crystals, with comments


  1. The structure of a bromomethane monolayer adsorbed on graphite S. M. Clarke & R. K. Thomas (1991) Mol. Phys
  2. The structures of 1-bromoheptane and 1-bromononane monolayers adsorbed on the surface of graphite C. Sun, S. M. Clarke, A. Brewer, B. Li, J. E. Parker & F. Demmel (2012) Mol. Phys
  3. The structure of a methyl iodide monolayer adsorbed on graphite R. E. Bucknall, S. M. Clarke, R. A. Shapton & R. K. Thomas (1989) Mol. Phys
  4. Adsorption of iodoalkanes on graphite Chenguang Sun, Adam Brewer, Stuart M. Clarke, Tej Bhinde & Julia E. Parker (2013) Mol. Phys
  5. A quantitative parameter for predicting mixing behaviour in adsorbed layers: the 2D isomorphism coefficient Stuart M.Clarke, Loic Messe, James Adams, Akira Inaba, Thomas Arnold & Robert K.Thomas (2003) Chem. Phys Letts
  6. Mixing in Adsorbed Monolayers:? Perfluorinated Alkanes J. E. Parker & S. M. Clarke (2008) Langmuir
  7. Phase separation of carboxylic acids on graphite surface at submonolayer regime M. D. Alba, A. K. Bickerstaffe, M. A. Castro, S. M. Clarke, S. Medina, C. Millan, M. M. Orta, E. Pavon & A. C. Perdigon (2009) Euro Phys. J
  8. Molecular orientation of carboxylic acids adsorbed on graphite from the liquid Stuart M. Clarke, Akira Inabe, Robert K. Thomas & Joe Fish (2001) J. Phys Soc Japan
  9. The Crystalline Structures of Carboxylic Acid Monolayers Adsorbed on Graphite A. K. Bickerstaffe, N. P. Cheah, S. M. Clarke, J. E. Parker, A. Perdigon, L. Messe, & A. Inaba (2006) J. Phys Chem
  10. Crystalline Monolayer of Dodecanoic Acid Adsorbed on Graphite from n-Heptane Solution Miguel A. Castro, Stuart M. Clarke, Akira Inaba, Chu C. Dong, & Robert K. Thomas (1998) J. Phys Chem
  11. Crystalline Structures of Alkylamide Monolayers Adsorbed on the Surface of Graphite Tej Bhinde, Stuart M. Clarke, Tamsin K. Phillips, Thomas Arnold, & Julia E. Parker (2010) Langmuir
  12. Thermodynamic Investigation of the Adsorption of Amides on Graphite from Their Liquids and Binary Mixtures Thomas Arnold & Stuart M. Clarke (2008) Langmuir
  13. To Mix or Not To Mix: 2D Crystallization and Mixing Behavior of Saturated and Unsaturated Aliphatic Primary Amides Kunal S. Mali, Bernard Van Averbeke, Tej Bhinde, Adam Y. Brewer, Thomas Arnold, Roberto Lazzaroni, Stuart M. Clarke, & Steven De Feyter (2011) ACS Nano
  14. Adsorption of Unsaturated Amides on a Graphite Surface: trans-Unsaturated Amides Tej Bhinde, Adam Y. Brewer, Stuart M. Clarke, Tamsin K. Phillips, Thomas Arnold, & Julia E. Parker (2011) J. Phys Chem
  15. Behavior of Binary Alcohol Mixtures Adsorbed on Graphite Using Calorimetry and Scanning Tunneling Microscopy Guojie Wang, Shengbin Lei, Steven De Feyter, Rebecca Feldman, Julia E. Parker, & Stuart M. Clarke (2008) Langmuir
  16. Mixing Behavior at the Solid/Liquid Interface:? Binary Alcohol Monolayers on Graphite Loic Messe, Stuart M. Clarke, Chucuan Dong, Robert K. Thomas, Akira Inaba, Maria D. Alba, & Miguel A. Castro (2002) Langmuir
  17. Mixing Behavior at the Solid/Liquid Interface:? Binary Monolayers of Linear Alcohols Adsorbed on Graphite Loic Messe, Stuart M. Clarke, Thomas Arnold, Chucuan Dong, Robert K. Thomas, & Akira Inaba (2002) Langmuir
  18. Combined Diffraction and Density Functional Theory Calculations of Halogen-Bonded Co-crystal Monolayers Marco Sacchi, Adam Y. Brewer, Stephen J. Jenkins, Julia E. Parker, Tomislav Friscic, & Stuart M. Clarke (2013) Langmuir
  19. Observation of a two-dimensional halogen-bonded cocrystal at sub-monolayer coverage using synchrotron X-ray diffraction Stuart M. Clarke, Tomislav Friscic, William Jones, Anasuya Mandal, Chenguang Sun & Julia E. Parker (2011) Chem. Comm
  20. 2D constraint modifies packing behaviour: a halobenzene monolayer with X3 halogen-bonding motif Jonathan A. Davidson, Stephen J. Jenkins, Fabrice Gorrec & Stuart M. Clarke (2021) Mol. Phys
  21. Halogen Bonding in Bicomponent Monolayers: Self-Assembly of a Homologous Series of Iodinated Perfluoroalkanes with Bipyridine Jonathan A. Davidson, Marco Sacchi, Fabrice Gorrec, Stuart M. Clarke, & Stephen J. Jenkins (2021) Langmuir