Nanoporous supramolecular networks physisorbed on solid surfaces have been extensively used to immobilize a variety of guest molecules. Host-guest chemistry in such two-dimensional (2D) porous networks is a rapidly expanding field due to potential applications in separation technology, catalysis and nanoscale patterning. Diverse structural topologies with high crystallinity have been obtained to capture molecular guests of different sizes and shapes. A range of non-covalent forces such as hydrogen bonds, van der Waals interactions, coordinate bonds have been employed to assemble the host networks. Recent years have witnessed a surge in the activity in this field with the implementation of rational design strategies for realizing controlled and selective guest capture. In this feature article, we review the development in the field of surface-supported host-guest chemistry as studied by scanning tunneling microscopy (STM). Typical host-guest architectures studied on solid surfaces, both under ambient conditions at the solution-solid interface as well as those formed at the ultrahigh vacuum (UHV)-solid interface, are described. We focus on isoreticular host networks, hosts functionalized pores and dynamic host-guest systems that respond to external stimuli.

Host–guest chemistry in two-dimensional supramolecular networks