Near Fermi superatom state stabilized by surface state resonances in a multiporous molecular network

Two-dimensional (2D) honeycomb molecular networks confine the substrate’s surface electrons within their pores, providing an ideal playground to investigate the quantum electron scattering phenomena. Besides surface state confinement, laterally protruding organic states can collectively hybridize at the smallest pores into superatom molecular orbitals (SAMOs). Although both types of pore states could be simultaneously hosted within nanocavities, their coexistence and possible interaction are unexplored. Here, we show that these two types of pore states do coexist within the smallest nanocavities of a 2D halogen-bonding multiporous network grown on Ag(111) studied. We find that SAMOs undergo an important stabilization when hybridizing with the confined surface states. These findings provide further control over the surface electronic structure exerted by 2D nanoporous systems.