Lithium-intercalation of phenyl-capped aniline dimers: A study by photoelectron spectroscopy and quantum-chemical calculations

Structural and electronic properties of pristine and lithium-intercalated, phenyl-capped aniline dimers as a model for the lithium-polyaniline system have been studied by photoelectron spectroscopy and quantum-chemical calculations. It was found that the electronic structure of reduced and oxidized forms of oligoanilines is only weakly affected by isomerism. Upon intercalation, charge transfer from the Li-atoms is remarkable and highly localized at N atomic sites where configurations are energetically favored in which both N-atoms of the dimers are bound to Li-atoms. Conversion of nitrogen sites is different for the two forms of aniline dimers and incomplete up to high intercalation levels indicating a pronounced role of solid state effects in the formation of such compounds.