Molecules consisting of a donor and an acceptor moiety can exhibit large intrinsic dipole moments. Upon deposition on a metal surface, the dipole may be effectively screened and the charge distribution altered due to hybridization with substrate electronic states. Here, we deposit ethyldiaminodicyanoquinone molecules, which exhibit a large dipole moment in the gas phase, on a Au(111) surface. Employing a combination of scanning tunneling microscopy and noncontact atomic force microscopy, we find that a significant dipole moment persists in the flat-lying molecules. Density functional theory calculations reveal that the dipole moment is even increased on the metal substrate as compared to the gas phase. We also show that the local contact potential across the molecular islands is decreased by several tens of meV with respect to the bare metal. We explain this by the induced charge-density redistribution due to the adsorbed molecules, which confine the substrate's wavefunction at the interface. Our local measurements provide direct evidence of this so-called push-back or cushion effect at the scale of individual molecules.

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Electrostatic potentials strongly affect molecular energy levels and charge states, providing the fascinating opportunity of molecular gating. Their influence on molecular vibrations remains less explored. Here, we investigate ethyl‐diaminodicyanoquinone molecules on a monolayer of MoS2 on Au(111) using scanning tunneling and atomic force microscopy and spectroscopy. These molecules exhibit a large dipole moment in gas phase, which is found to (partially) persist on the MoS2 monolayer. The self‐assembled structures consist of chains, where the dipoles of neighboring molecules are aligned antiparallel. Thanks to the decoupling efficiency of the molecular states from the metal by the MoS2 interlayer, vibronic states of the molecules are resolved, which vary in intensity depending on the molecular surrounding. We suggest that the vibrations are strongly damped by electrostatic interactions with the environment.

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