TiO₂(110) Charge Donation to an Extended π‑Conjugated Molecule

The surface reduction of rutile TiO₂(110) generates a state in the band gap whose excess electrons are spread among multiple sites, making the surface conductive and reactive. The charge extraction, hence the surface catalytic properties, depends critically on the spatial extent of the charge redistribution, which has been hitherto probed by small molecules that recombine at oxygen vacancy (O_vac) sites. We demonstrate by valence band resonant photoemission (RESPES) a very general charge extraction mechanism from a reduced TiO₂(110) surface to an extended electron-acceptor organic molecule. Perylene-tetra-carboxylic-diimide (PTCDI) is not trapped at O_vac sites and forms a closely packed, planar layer on TiO₂(110). In this configuration, the perylene core spills out the substrate excess electrons, filling the lowest unoccupied molecular orbital (LUMO). The charge transfer from the reduced surface to an extended π-conjugated system demonstrates the universality of the injection/extraction mechanism, opening new perspectives for the coupling of reducible oxides to organic semiconductors and supported catalysts

Noncontact Layer Stabilization of Azafullerene Radicals: Route toward High-Spin-Density Surfaces

We deposit azafullerene C59N• radicals in a vacuum on the Au(111) surface for layer thicknesses between 0.35 and 2.1 monolayers (ML). The layers are characterized using X-ray photoemission (XPS) and X-ray absorption fine structure (NEXAFS) spectroscopy, low-temperature scanning tunneling microscopy (STM), and by density functional calculations (DFT). The singly unoccupied C59N orbital (SUMO) has been identified in the N 1s NEXAFS/XPS spectra of C59N layers as a spectroscopic fingerprint of the molecular radical state. At low molecular coverages (up to 1 ML), films of monomeric C59N are stabilized with the nonbonded carbon orbital neighboring the nitrogen oriented toward the Au substrate, whereas in-plane intermolecular coupling into diamagnetic (C59N)2 dimers takes over toward the completion of the second layer. By following the C59N• SUMO peak intensity with increasing molecular coverage, we identify an intermediate high-spin-density phase between 1 and 2 ML, where uncoupled C59N• monomers in the second layer with pronounced radical character are formed. We argue that the C59N• radical stabilization of this supramonolayer phase of monomers is achieved by suppressed coupling to the substrate. This results from molecular isolation on top of the passivating azafullerene contact layer, which can be explored for molecular radical state stabilization and positioning on solid substrates