Molecular self-assembly is a versatile nanofabrication technique with atomic precision en route to molecule-based electronic components and devices. Here, we demonstrate a three-dimensional, bicomponent supramolecular network architecture on an all-carbon sp(2)-sp(3) transparent platform. The substrate consists of hydrogenated diamond decorated with a monolayer graphene sheet. The pertaining bilayer assembly of a melamine-naphthalenetetracarboxylic diimide supramolecular network exhibiting a nanoporous honeycomb structure is explored via scanning tunneling microscopy initially at the solution-highly oriented pyrolytic graphite interface. On both graphene-terminated copper and an atomically flat graphene/diamond hybrid substrate, an assembly protocol is demonstrated yielding similar supramolecular networks with long-range order. Our results suggest that hybrid platforms, (supramolecular) chemistry and thermodynamic growth protocols can be merged for in situ molecular device fabrication.
Chiroptically active allenes are employed for the construction of surface-confined nanostructures. Morphological complementarity between the homochiral units leads to self-assembly of two highly-ordered, upstanding, diastereomeric architectures. The novel, intertwined self-assembled layer structures feature reactive terminal alkynes for further functionalization and carry potential for widespread applications exploiting chiroptical amplification.
Two flexible multivalent molecular units are employed to self-assemble highly regular supramolecular porous networks at the solid/liquid interface. Scanning tunnelling microscopy imaging corroborated with molecular dynamics simulations make it possible to elucidate the conformational freedom behind the binding motif, which identify the architecture as a highly regular soft network.
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.
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