Supramolecular assembly requires non-covalent interactions directing the formation of 2D polymers by relying on electrostatic interactions such as hydrogen bonding and van der Waals forces. To design artificial assemblies capable of high selectivity requires correct manipulation of energetic and stereochemical features of non-covalent forces.  Some benefits of non-covalent interactions is their reversible nature and response to external factors such as temperature and concentration. The mechanism of non-covalent polymerization in supramolecular chemistry is highly dependent on the interactions during the self-assembly process. The degree of polymerization depends highly on temperature and concentration. The mechanisms may be divided into three categories: isodesmic, ring-chain, and cooperative.
One example of isodesmic associations in supramolecular aggregates is seen in Figure 7, (CA*M) cyanuric acid (CA) and melamine (M) interactions and assembly through hydrogen bonding. Hydrogen bonding has been used to guide assembly of molecules into two-dimensional networks, that can then serve as new surface templates and offer an array of pores of sufficient capacity to accommodate large guest molecules.  An example of utilizing surface structures through non-covalent assembly uses adsorbed monolayers to create binding sites for target molecules through hydrogen bonding interactions. Hydrogen bonding is used to guide the assembly of two different molecules into a 2D honeycomb porous network under ultra high vacuum seen in figure 8. 2D polymers based on DNA have been reported