Out?Of?Plane Metal Coordination for a True Solvent?Free Building with Molecular Bricks: Dodging the Surface Ligand Effect for On?Surface Vacuum Self?Assembly

The desirable self-assembly (SA) of repeated 2D stacked layers requires a “holistic analysis” three interconnected components: the electrode, interface, and molecular component; among them, contact interface bears largest burden responsibilities. Epitaxial growth (EG) coherent 2D+n heterojunction by solvent-free deposition holds great promise, although feasibility has never been demonstrated given multiple drawbacks (e.g., surface-ligand effect, SLE). Here, it is how (n = 3) layered heterorganic film grown on an archetypal Fe metal electrode. groundbreaking achievement result in-vacuum integration of: i) chemical decoupling basal organic layer (a ZnII-tetraphenylporphyrine, ZnTPP) from ii) 2D-ordering ZnTPP commensurate to substrate, iii) rigid, stoichiometric, orthogonally arranged, molecule-to-molecule coupling between ditopic linear bridging ligand (i.e., DPNDI) guided SA coordination chemistry, iv) sharp (chemical) termination film.