The self-assembly of nanometer-sized building blocks on surfaces and at interfaces is a powerful way to fabricate complex molecular nanostructures following the bottom-up principle. Surface-confined two-dimensional (2D) molecular networks, especially those with void spaces, so-called “2D porous networks”, attract a lot of interest. These 2D porous networks are used as hosts to immobilize functional units as guest molecules in a repetitive and spatially ordered arrangement, and also as platform for the construction of molecular devices. The size and geometry of the pores, actually nanowells, in the networks could be easily tailored by adjusting the size and symmetry of the building blocks as well as the substrate. Among them the networks formed by alkoxylated dehydrobenzo annulenes (DBAs) via alkyl chain interdigitation represent an interesting case. The flexibility of the alkyl chains and the weak van der Waals interactions between them make the supramolecular network quite flexible. These networks were observed to change their structure not only in response to the inclusion of ’static’ guest molecules, but also in response to the dynamics of clusters of guest molecules captured in the nanowells. (CryEngComm, 2010, 12, 3369-3381, Chem. Commun., 2010, 46, 9125-9127).
Molecular recognition at interfaces involves many simultaneous interactions based on molecular shape, size, functional groups, etc. When a binary mixture is applied to a interface the recogonition between similar molecule determines the phase behavior of the mixture. Collaborated with researchers from Katholieke Universiteit Leuven, Osaka University and Maria-Curie Skłodowska University professor Shengbin Lei’s group has systematically investigated the mixing behavior of molecules (DBAs) with different alkyl substituents at the solid-liquid interface to reveal the phase behavior of complex systems. Scanning tunneling microscopy and Monte Carlo simulations demonstrate that the phase behavior of binary mixtures of alkylated DBAs at the solid-liquid interface can be predicted by the 2D isomorphism coefficient. In addition we also investigated the influence of coadsorption of template molecules on the phase behavior of DBA mixtures. Co-adsorption of these molecules significantly promotes mixing of DBAs, possibly by affecting the recognition between alkyl chains. Monte Carlo simulations proof that the 2D isomorphism coefficient can predict the phase behavior at the interface. These results are helpful for the understanding of phase behavior of complex assembling systems and also for the design of programmable porous networks and hierarchical architectures at the solid-liquid interface. (ACS nano, 2011, 5, 4145-4157).