(50f) Molecular Self-Assembly of Organometallic Complexes on 2D Materials: A Molecular Dynamics Study

Molecular self-assembly on solid surfaces is an effective bottom-up technique to synthesize ordered and novel functional nanomaterials. In addition to nanoparticles and polymeric building blocks, there are numerous organic and inorganic molecules exhibiting great potential to form functional nanomaterials via controllable self-assembly. For instance, organometallic complexes and transition metal compounds are among top candidates for this aim, owing to their highly covalent metal-carbon bonds as well as their hydrogen bonds that drive the self-assembly. However, adjusting the interplay between molecule-molecule and molecule-substrate is the key challenge that determines the final structure.

In this work, using molecular dynamics simulations, we investigate the molecular self-assembly of three different organometallic compounds, namely magnesium porphyrin (MgP), cobalt phthalocyanine (CoPc), and ferrocenecarboxylic acid (FcCOOH), on graphene and h-BN substrates. Thermodynamics and kinetics of the self-assembled structures are studied and the final lattice structure of MgP on graphene and CoPc on graphene/h-BN substrates as well as the quasi-crystalline structure of FcCOOH on graphene are characterized at different operating conditions and compared with experimental observations. The simulation results can be used for rational design of novel functional nanomaterials based on self-assembled structures of organometallic molecules on 2D materials.