Long?Range Surface?Assisted Molecule?Molecule Hybridization

Metalated phthalocyanines (Pc's) are robust and versatile molecular complexes, whose properties can be tuned by changing their functional groups central metal atom. The electronic structure of magnesium Pc (MgPc) - structurally electronically similar to chlorophyll adsorbed on the Ag(100) surface is investigated low-temperature scanning tunneling microscopy (STM) spectroscopy (STS), non-contact atomic force (ncAFM) density theory (DFT). Single, isolated MgPc's exhibit a flat, four-fold rotationally symmetric morphology, with doubly degenerate, partially populated (due surface-to-molecule electron transfer) lowest unoccupied orbitals (LUMOs). In contrast, neighbouring molecules in proximity undergo lift LUMOs degeneracy, near-Fermi local states reduced two-fold rotational symmetry, indicative long-range attractive intermolecular interaction. latter assigned surface-mediated two-step hybridization process. First, interact conduction electrons, forming hybrid molecule-surface enhanced spatial extension. Then, these delocalized further hybridize those molecules. This work highlights how adsorbates including orbital degeneracies symmetries significantly altered via hybridization, over extended distances (beyond 3 nm), having important implications for prospects molecule-based solid-state technologies.