Observation of SOMO-HOMO Inversion in a Neutral Polycyclic Conjugated Hydrocarbon

We report the generation of a nonbenzenoid polycyclic conjugated hydrocarbon, which consists of a biphenyl moiety substituted by indenyl units at the 4,4′ positions, on ultrathin sodium chloride films by tip-induced chemistry. Single-molecule characterization by scanning tunneling and atomic force microscopy reveals an open-shell biradical ground state with a peculiar electronic configuration wherein the singly occupied molecular orbitals (SOMOs) are lower in energy than the highest occupied molecular orbital (HOMO).