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 and central metal atom. The electronic structure of magnesium Pc (MgPc)—structurally and electronically similar to chlorophyll—adsorbed on the Ag(100) surface is investigated by low‐temperature scanning tunneling microscopy and spectroscopy, non‐contact atomic force microscopy, and density functional theory. Single, isolated MgPc's exhibit a flat, fourfold rotationally symmetric morphology, with doubly degenerate, partially populated (due to surface‐to‐molecule electron transfer) lowest unoccupied molecular orbitals (LUMOs). In contrast, MgPc's with neighbouring molecules in proximity undergo a lift of LUMOs degeneracy, with a near‐Fermi local density of states with reduced twofold rotational symmetry, indicative of a long‐range attractive intermolecular interaction. The latter is assigned to a surface‐mediated two‐step electronic hybridization process. First, LUMOs interact with Ag(100) conduction electrons, forming hybrid molecule‐surface orbitals with enhanced spatial extension. Then, these delocalized molecule‐surface states further hybridize with those of neighbouring molecules. This work highlights how the electronic structure of molecular adsorbates—including orbital degeneracies and symmetries—can be significantly altered via surface‐mediated intermolecular hybridization, over extended distances (beyond 3 nm), having important implications for prospects of molecule‐based solid‐state technologies. On a silver surface, magnesium phthalocyanine molecules undergo a perturbation of their electronic structure as a result of an attractive interaction with their nearest‐neighbors. Quantitative agreement with supporting theoretical modelling indicates that this interaction consists of multiple‐nanometer‐range intermolecular hybridization enabled by the underlying substrate. These observations offer new possibilities to control electronic properties for engineered nanomaterials.