On-surface synthesis of single-layered two-dimensional covalent organic frameworks via solid-vapor interface reactions

J Am Chem Soc. 2013 Jul 17;135(28):10470-4. doi: 10.1021/ja403464h. Epub 2013 Jul 3.


Surface covalent organic frameworks (SCOFs), featured by atomic thick sheet with covalently bonded organic building units, are promised to possess unique properties associated with reduced dimensionality, well-defined in-plane structure, and tunable functionality. Although a great deal of effort has been made to obtain SCOFs with different linkages and building blocks via both "top-down" exfoliation and "bottom-up" surface synthesis approaches, the obtained SCOFs generally suffer a low crystallinity, which impedes the understanding of intrinsic properties of the materials. Herein, we demonstrate a self-limiting solid-vapor interface reaction strategy to fabricate highly ordered SCOFs. The coupling reaction is tailored to take place at the solid-vapor interface by introducing one precursor via vaporization to the surface preloaded with the other precursor. Following this strategy, highly ordered honeycomb SCOFs with imine linkage are obtained. The controlled formation of SCOFs in our study shows the possibility of a rational design and synthesis of SCOFs with desired functionality.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Graphite / chemistry*
  • Models, Molecular
  • Organic Chemicals / chemical synthesis*
  • Organic Chemicals / chemistry
  • Quantum Theory
  • Surface Properties
  • Thermodynamics
  • Volatilization


  • Organic Chemicals
  • Graphite