Correlation of Work Function and Conformation of C₈₀ Endofullerenes on h‐BN/Ni(111)

Abstract Change of conformation or polarization of molecules is an expression of their functionality. If the two correlate, electric fields can change the conformation. In the case of endofullerene single‐molecule magnets the conformation is linked to an electric and a magnetic dipole moment, and therefore magnetoelectric effects are envisoned. The interface system of one monolayer Sc₂TbN@C₈₀ on hexagonal boron nitride (h‐BN) on Ni(111) has been studied. The molecular layer is hexagonally close packedbut incommensurate. With photoemission the polarization and the conformation of the molecules are addressed by the work function and angular intensity distributions. Valence band photoemission (ARPES) shows a temperature‐induced energy shift of the C₈₀ molecular orbitals that is parallel to a change in work function of 0.25 eV without charging the molecules. ARPES indicates a modification in molecular conformations between 30 and 300 K. This order–disorder transition involves a polarization change in the interface and is centered at 125 K as observed with high‐resolution X‐ray photoelectron spectroscopy (XPS). The temperature dependence is described with a thermodynamic model that accounts for disordering with an excitation energy of 74 meV into a high entropy ensemble. All experimental results are supported by density functional theory (DFT).