Modeling of the 2D self-assembly of tripod-shaped functional molecules with patchy interaction centers

Surface-confined self-assembly of star-shaped functional molecules has been recently recognized as a promising method to fabricate extended superstructures with predefined architectures and physico-chemical functions. In this work we use the Monte Carlo (MC) method to explore 2D self-assembly of rigid tripod-shaped tectons equipped with patchy interaction centers located at the ends of molecular arms. These angular interaction zones represent terminal functional groups, which due to some flexibility/extended size, can provide intermolecular bonds which does not have to be collinear with the arms. Our main focus is on the effect of angular diameter of the interaction centers on the morphology of the simulated assemblies. Moreover, we explore the influence of molecular backbone symmetry on the periodicity and connectivity of the resulting adsorbed superstructures. The obtained results are compared with their selected counterparts from lattice MC simulations. It is demonstrated that a suitable choice of the size of the interaction centers and backbone aspect ratio allows for directing the self-assembly towards 2D networks comprising pores of different size and shape. The results from our theoretical modeling can be helpful in designing new functional organic building blocks able to form supramolecular networks with desired structural properties.