The function of surface-bound assemblies is often dependent on various factors including intramolecular interactions, molecular orientation, and packing. In addition, formation and understanding of defects and grains, and the interfacing of the nanofabricated nanostructures to the macroscopic outside world are still major issues that need to be resolved. Therefore, it is a tremendous challenge to a priori design molecular-based materials with a set of predetermined properties and/or functions.