Layer-By-Layer Epitaxy Of Porphyrin-Ligand Fe(Ii)-Fe(Iii) Nanoarchitectures For Advanced Metal-Organic Framework Growth

Precisely layered molecular heterostructures are promising but still largely unexplored materials, with the potential to complement and enhance the scope of two-dimensional heterostructures. The controlled epitaxial growth of vertically stacked molecular layers connected through tailored linkers, can lead to significant development in the field. Here, we demonstrate that sequential assembly of prototypical iron porphyrins and axial ligands can be steered via temperature-programmed desorption, and monitored by mass spectrometry and by high-resolution atomic force microscopy under ultrahigh vacuum conditions. Complementary photoelectron spectroscopy analysis delivers chemical insight into the formation of layer-by-layer nanoarchitectures. Our temperature-directed methodology outlines a promising strategy for the in vacuo fabrication of precisely stacked, multicomponent (metal-organic) molecular heterostructures.