An electron acceptor molecule in a nanomesh: F 4 TCNQ on h -BN/Rh(111)

•The interesting charge transfer effects between F4TCNQ(C12F4N4) molecules and hexagonal boron nitride nanomesh (h-BN/Rh(111)) are demonstrated based on photoemission spectroscopy.•Upon increasing molecular coverage, the work function of the F4TCNQ/h−BN/Rh system increases, indicating electron transfer from the substrate to the F4TCNQ molecules.•The σα and σβ bands of the h-BN nanomesh shift towards lower and higher binding energy individually upon charging. The molecules prefer to adsorb inside of the pores.•Density functional theory calculations indicate the lowest energy structure is doubly charged F4TCNQ2− in the nanomesh pores.•F4TCNQ molecules display high mobility and molecular “hopping” on the h -BN surface is observed at room temperature.